CN117186633A - Modified polyamide and preparation method and application thereof, and modified polyamide product - Google Patents
Modified polyamide and preparation method and application thereof, and modified polyamide product Download PDFInfo
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- CN117186633A CN117186633A CN202210629357.0A CN202210629357A CN117186633A CN 117186633 A CN117186633 A CN 117186633A CN 202210629357 A CN202210629357 A CN 202210629357A CN 117186633 A CN117186633 A CN 117186633A
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- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
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- 238000006243 chemical reaction Methods 0.000 claims description 87
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 54
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 229910002804 graphite Inorganic materials 0.000 claims description 32
- 239000010439 graphite Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- 238000002844 melting Methods 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- 150000004985 diamines Chemical class 0.000 claims description 18
- 229910021389 graphene Inorganic materials 0.000 claims description 18
- 229920006141 Polyamide 5X Polymers 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 11
- 238000001764 infiltration Methods 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 230000008595 infiltration Effects 0.000 claims description 9
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 4
- 238000005452 bending Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000299 Nylon 12 Polymers 0.000 claims description 2
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 2
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- 125000004427 diamine group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 47
- 239000011347 resin Substances 0.000 description 47
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 34
- 238000001816 cooling Methods 0.000 description 33
- 229920006122 polyamide resin Polymers 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 239000012299 nitrogen atmosphere Substances 0.000 description 21
- 239000001361 adipic acid Substances 0.000 description 17
- 235000011037 adipic acid Nutrition 0.000 description 17
- 230000000694 effects Effects 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 15
- 239000000498 cooling water Substances 0.000 description 14
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 14
- 238000007599 discharging Methods 0.000 description 13
- 239000000155 melt Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000010907 mechanical stirring Methods 0.000 description 7
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229920006145 PA516 Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
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- Polyamides (AREA)
Abstract
The invention discloses a modified polyamide, a preparation method and application thereof, and a modified polyamide product. The modified polyamide of the invention comprises a polyamide matrix and conductive materials distributed in the polyamide matrix, wherein the mass ratio of the conductive materials to the polymerization raw materials of the polyamide matrix is (0.5-15): 100, and the volume resistivity of the modified polyamide is 1 multiplied by 10 4 ～9×10 7 Omega.m. The modified polyamide of the invention has the advantages of less addition of conductive materials, good antistatic performance and simultaneouslyHas good mechanical properties and improves the processability.
Description
Technical Field
The invention particularly relates to modified polyamide, a preparation method and application thereof, and a modified polyamide product.
Background
Polyamide, commonly known as Nylon, is a generic term for thermoplastic resins containing recurring amide groups (-NHCO-) in the molecular chain, and is prepared by dehydrating polycondensation of a dibasic acid and a diamine, or by dehydrating an amino acid (or an amino acid derivative) to prepare a lactam, and then ring-opening polymerization. The polyamide has excellent mechanical property, processability, wear resistance, chemical resistance and other properties, and is mainly applied to fibers and engineering plastics, and a small amount of the polyamide is used for preparing films.
Along with the gradual expansion of application fields, the requirements on special functionalization of polyamide are also higher and higher, and the polyamide material with antistatic performance is one of novel polyamide materials, and is mostly formed by blending conductive carbon black or graphite with polyamide resin and the like. In order to ensure antistatic performance, the addition amount of the conductive carbon black or graphite in the composite material is large, the percolation threshold is about 20wt%, and although the conductive performance is improved, the conductive carbon black or graphite also has more defects in practical application, for example, when the conductive carbon black or graphite is used as a spinning material, the spinning performance is poor; when applied as engineering plastics, large amounts of carbon black and graphite can also lead to changes in the composition of the polyamide, which in turn lead to poorer physical properties and processability, which seriously affect the application of the conductive polyamide material.
Disclosure of Invention
The invention solves the technical problems of overcoming the defect of poor material performance or processability caused by larger addition amount of conductive materials in antistatic polyamide in the prior art, and provides a polyamide melt, a polyamide resin, a preparation method, an application and a polyamide product. The modified polyamide has the advantages of less addition of conductive materials, good antistatic property, good mechanical property and improved processability.
The invention solves the technical problems by the following technical proposal:
the invention provides a modified polyamide comprising a polyamide matrix and a polymer dispersed in the polyamide matrixA conductive material, wherein the mass ratio of the conductive material to the polymer raw material of the polyamide matrix is (0.5-15): 100, and the volume resistivity of the modified polyamide is 1 x 10 4 ～9×10 7 Ω·m。
In the present invention, the conductive material may be conventional in the art, preferably a carbon-based conductive material.
Wherein the carbon-based conductive material may be conventional in the art, preferably one or more of conductive carbon black, graphite, expanded graphite, graphite oxide, graphene oxide and graphene.
The graphite oxide may be of a type conventional in the art, such as a type SE2430W-N graphite oxide manufactured by Hexacum sixth element materials technologies Co.
The preparation method of the graphite oxide can be conventional in the art and is generally obtained by treating graphite with a strong oxidizing agent.
As is well known to those skilled in the art, the expanded graphite generally refers to a loose porous vermiform material obtained by volumetric expansion of natural crystalline flake graphite.
The expanded graphite may be of a standard type conventional in the art, and may be, for example, an expanded graphite of type YH-8 manufactured by Qingdao rock-sea carbon materials Co., ltd.
The original expanded volume of the expanded graphite may be conventional in the art and may generally be in the range of 400 to 650ml/g, for example 600ml/g.
As is well known to those skilled in the art, the graphene oxide generally refers to an oxide of graphene, and the surface of the oxide contains oxygen-containing functional groups.
The preparation method of graphene oxide is not particularly limited.
The specification model of the graphene oxide may be conventional in the art, for example, may be a model MC-18 graphene oxide manufactured by Qingdao rock-sea carbon materials Co.
In one embodiment, graphene or graphene oxide is preferable as the conductive material, and the resulting modified polyamide has a better antistatic effect.
In the present invention, the polyamide matrix may be conventional in the art and may be generally one or more of nylon 6, nylon 66, nylon 12, nylon 46, nylon 610, nylon 612, nylon l010, polyamide 5X/5T and polyamide 5X/5I, preferably one or more of polyamide 5X, polyamide 5X/5T, polyamide 5X/5I and nylon 66.
Wherein the polyamide 5X may be a polyamide obtained by polycondensation of 1, 5-pentanediamine and an aliphatic dibasic acid, which is conventional in the art.
The aliphatic dibasic acid has preferably any of 4 to 18 carbon atoms, more preferably 6, 4, 10, 12 or 16 carbon atoms.
It is conventionally understood in the art that polyamide 510 is a polyamide obtained by polycondensation of 1, 5-pentanediamine and sebacic acid.
It is generally understood in the art that polyamide 512 is a polyamide obtained by polycondensation of 1, 5-pentanediamine and lauryldiacid.
As is conventionally understood in the art, polyamide 516 is a polyamide obtained by polycondensation of 1, 5-pentanediamine and hexadecanedioic acid.
Wherein, it is conventionally understood in the art that the polyamide 5X/5T is a polyamide obtained by polycondensation of 1, 5-pentanediamine, an aliphatic dibasic acid having X carbon atoms and terephthalic acid.
In the polyamide 5X/5T, the X is preferably any integer of 4 to 18, more preferably 6.
In certain preferred embodiments of the present invention, the polyamide 5X/5T is polyamide 56/5T.
Among them, it is conventionally understood in the art that the polyamide 5X/5I is a polyamide obtained by polycondensation of 1, 5-pentanediamine, an aliphatic dibasic acid having X carbon atoms and isophthalic acid.
In the polyamide 5X/5I, the X is preferably any integer of 4 to 18, more preferably 6.
In certain preferred embodiments of the present invention, the polyamide 5X/5I is polyamide 56/5I.
In the present invention, it is conventionally understood by those skilled in the art that the polyamide matrix is obtained by dehydrating polycondensation of the polymerization raw material.
In the present invention, the polymerization raw material may be conventional in the art, and preferably includes diamine and diacid.
Wherein the diamine may be any one of terminal diamines having 1 to 10 carbon atoms, such as butanediamine, hexanediamine or 1, 5-pentanediamine, as is conventional in the art.
Wherein the diacid may be conventional in the art, preferably an aliphatic diacid, a mixture of an aliphatic diacid and terephthalic acid, or a mixture of an aliphatic diacid and isophthalic acid.
The aliphatic dibasic acid has preferably any of 4 to 18 carbon atoms, more preferably 6, 4, 10, 12 or 16 carbon atoms.
Wherein the molar ratio of the diamine to the diacid may be conventional in the art, preferably (0.9-1.2): 1, more preferably (1-1.2): 1, for example 1.01:1, 1.02:1, 1.03:1, 1.04:1, 1.06:1 or 1.07:1.
Where the diamine is 1, 5-pentanediamine and the diacid is adipic acid, the molar ratio of the diamine to the diacid may be conventional in the art, preferably (0.9 to 1.1): 1, more preferably (1 to 1.05): 1, for example 1.02:1, 1.01:1.
Wherein the diamine is 1, 5-pentanediamine, and the diacid is adipic acid and terephthalic acid, the molar ratio of the diamine to the diacid may be conventional in the art, preferably (1-1.2): 1, more preferably 1.1:1.
Wherein the diamine is 1, 5-pentanediamine, and the diacid is sebacic acid, the molar ratio of the diamine to the diacid can be conventional in the art, preferably (1-1.1): 1, more preferably 1.03:1.
Wherein the diamine is 1, 5-pentanediamine, and the diacid is lauryldiacid, the molar ratio of the diamine to the diacid can be conventional in the art, preferably (1-1.15): 1, more preferably 1.06:1.
Wherein the diamine is 1, 5-pentanediamine, and the diacid is hexadecanoic diacid, the molar ratio of the diamine to the diacid can be conventional in the art, preferably (1-1.15): 1, more preferably 1.04:1.
In the present invention, the mass ratio of the conductive material to the polymerization raw material of the polyamide matrix is preferably (1 to 10): 100, more preferably (1.5-6): 100, for example 3.5:100, 5.5:100, 5.7:100, 6:100 or 6.5:100.
In the present invention, the volume resistivity is preferably 1×10 4 ～9×10 6 Omega.m, more preferably 7.8X10 4 ～8.4×10 6 Ω·m。
In the present invention, the modified polyamide preferably has a tensile strength of 51 to 94MPa.
In the present invention, the elongation at break of the modified polyamide is preferably 3.8 to 243%.
In the present invention, the modified polyamide preferably has a flexural strength of 95 to 107MPa.
In the present invention, the modified polyamide preferably has a notched impact strength of 5.1 to 6.2KJ/m2.
In the present invention, the melting point of the modified polyamide is preferably 194 to 310 ℃, more preferably 194 to 290 ℃, still more preferably 194 to 268 ℃.
In the present invention, the modified polyamide preferably has a relative viscosity of 2.33 to 2.51.
The invention also provides a preparation method of the modified polyamide, which comprises the following steps: the mixture comprising polyamide salt and the conductive material is subjected to polymerization reaction; the polyamide salt is the product of the reaction of the polymeric raw materials in water.
The antistatic polyamide material in the prior art is obtained by blending polyamide resin and a conductive material, the dispersibility of the conductive material in a resin matrix is poor, a conductive network cannot be formed under the condition of low addition amount, the conductivity is poor, and the antistatic effect is poor. The invention creatively discovers that the addition of the conductive material in the polyamide synthesis process can effectively reduce the interface effect of the conductive material and the polyamide resin matrix and improve the dispersibility of the conductive material in the resin matrix, so that better conductivity and antistatic effect can be achieved under lower addition amount, and the prepared modified polyamide has good antistatic effect and mechanical property and improves the processability.
In the present invention, the concentration of the polyamide salt solution may be conventional in the art, preferably 30 to 90wt%, more preferably 50 to 75wt%.
In certain preferred embodiments of the present invention, the concentration of the polyamide salt solution is 30wt%, 40wt%, 41wt%, 45wt%, 47wt%, 75wt% or 90wt%.
In the present invention, the pH of the polyamide salt solution at the dilution to a concentration of 10wt% is preferably 6.5 or more, more preferably 6.3 to 9.2, still more preferably 7.2 to 9.2, for example 8.1, 8.3, 8.5 or 8.8.
The inventor researches find that the pH optimal selection range defined above can further improve the dispersion effect of the conductive material, thereby improving the antistatic effect.
In the present invention, the mixture may be obtained by methods conventional in the art, and may be generally any of the following modes:
mode one: the conductive material, the polymerization raw material and water are mixed and reacted;
mode two: and mixing the polymerization raw material with water, reacting to generate a polyamide salt solution, and mixing with the conductive material.
Preferably, the first mode and the second mode are each independently performed under an inert atmosphere. The inert atmosphere may be conventional in the art, preferably nitrogen.
Preferably, the mixing in the first mode and the second mode is performed by a method conventional in the art, and stirring is generally performed.
The stirring time in the first mode may be conventional in the art, preferably 1 to 3 hours, more preferably 2 hours.
The stirring time in mode two may be conventional in the art, preferably 1 to 3 hours, more preferably 2 hours.
In the present invention, the mixture is preferably further subjected to a step of infiltration before the polymerization reaction is performed.
Wherein, the infiltration can be carried out by a method conventional in the art, and is generally carried out by standing.
Wherein the time of the infiltration is preferably 6 to 20 hours, more preferably 8 to 12 hours, for example 11 hours.
The inventor researches find that the infiltration process of the conductive material and the polyamide salt solution before the polymerization reaction can further promote the dispersion of the conductive material, thereby improving the antistatic effect.
Wherein the steps of dispersing are preferably further included after the infiltrating and before the polymerization reaction.
The dispersion may be carried out by methods conventional in the art, preferably ultrasonic dispersion.
The time of the ultrasonic dispersion may be conventional in the art, preferably 1 to 5 hours, more preferably 3 hours.
The ultrasonic power in the ultrasonic dispersion may be conventional in the art, preferably 500 to 800W, more preferably 650W.
The ultrasonic dispersing apparatus may be conventional in the art, preferably a cell breaker.
In the present invention, the polymerization reaction can be carried out by a method conventional in the art, preferably a solution polymerization method, more preferably according to the following procedure: and (3) carrying out pressure maintaining reaction under the initial pressure, reducing the pressure to the intermediate pressure, carrying out pressure maintaining reaction, vacuumizing, and carrying out pressure maintaining reaction.
Wherein the initial pressure is preferably 0.5-3MPa, more preferably 0.8-2.2 MPa, for example 1.5MPa, 1.55MPa, 1.65MPa, 1.7MPa or 2.1MPa, wherein the pressures are all gauge pressures.
Wherein the pressure maintaining can be performed by a method conventional in the art, and generally can be achieved by venting.
Wherein the temperature at the end of the hold at the initial pressure may be conventional in the art, preferably 200-300 ℃, more preferably 232-265 ℃, such as 235 ℃, 238 ℃, 241 ℃ or 243 ℃.
Wherein the intermediate pressure may be conventional in the art, preferably 0 to 0.2MPa, more preferably 0 to 0.15MPa, for example 0.02MPa, 0.06MPa, 0.08MPa or 0.1MPa, wherein the pressures are all gauge pressures.
The time for the pressure maintaining reaction at the intermediate pressure may be conventional in the art, and is preferably 2 to 30min, for example, 5min, 8min or 13min.
The temperature at the end of the hold of the intermediate pressure may be conventional in the art, preferably 200 to 350 ℃, more preferably 245 to 320 ℃, for example 247, 265, 267 or 307 ℃.
Wherein, the pressure after the vacuum pumping can be conventional in the art, and is preferably-0.005 to-0.12 MPa, more preferably-0.01 to-0.09 MPa, for example-0.07 MPa, -0.085MPa, -0.083MPa or-0.06 MPa.
The time for the pressure maintaining reaction after the vacuum pumping can be conventional in the art, preferably 8-42 min, for example 8, 13, 14min or 15min.
Wherein the temperature at the end of the pressure maintaining reaction after the vacuum pumping may be conventional in the art, preferably 260 to 330 ℃, such as 265 ℃, 281 ℃, 285 ℃, 308 ℃, 323 ℃, or 330 ℃.
In the present invention, it is generally understood by those skilled in the art that the product directly obtained after the polymerization reaction is referred to as a modified polyamide melt.
In the present invention, the polymerization reaction may further include a cooling step.
Those skilled in the art will appreciate that the product obtained after the cooling step is generally referred to as a modified polyamide resin.
Wherein the cooling may be carried out by methods conventional in the art, preferably water cooling.
The temperature of the cooling water used for the water cooling may be conventional in the art, preferably 10 to 40 ℃, more preferably 10 to 35 ℃, such as 10 ℃, 15 ℃, 18 ℃, 23 ℃, 27 ℃, 30 ℃, 33 ℃, or 35 ℃.
Wherein the cooling step may preferably be followed by a granulation or slicing step.
The invention also provides the modified polyamide prepared by the preparation method.
The invention also provides application of the modified polyamide in antistatic materials.
The invention also provides a modified polyamide product which is obtained by processing and molding the modified polyamide.
The process of the process molding can be conventional in the art, and can be injection molding, extrusion molding, blow molding or vacuum molding in general.
Wherein, when the modified polyamide is in the form of a resin, the method generally further comprises a step of melting the resin before the molding.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
(1) The modified polyamide or the modified polyamide product of the invention can realize good conductivity and antistatic effect under the condition of adding a small amount of conductive material, and the volume resistivity can be in the order of 10 4～7 In the range, it is shown that the antistatic effect is excellent.
(2) The modified polyamide or the modified polyamide product has excellent mechanical properties, and the tensile strength can be higher than 50MPa, even up to 94MPa; elongation at break can be higher than 3.8% and even up to 243%; the bending strength can be higher than 85MPa, even up to 107MPa; the notched impact strength can be higher than 5KJ/m 2 Even up to 6.3KJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The physical properties are basically equivalent to those of polyamide without conductive material, and the processability is strong.
(3) The relative viscosity and melting point are substantially comparable to polyamides without added conductive material.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The graphite, expanded graphite, graphite oxide, graphene oxide and graphene used in examples and comparative examples are all commercial powders having a particle size of 5 to 15 μm; wherein the original expansion volume of the expanded graphite is 600ml/g, and other raw materials are all commercially available.
Example 1
Preparation of antistatic Polyamide 56 resin
(1) 1, 5-pentanediamine, adipic acid and water were uniformly mixed under a nitrogen atmosphere to prepare a 75wt% polyamide salt solution. The molar ratio of 1, 5-pentanediamine to adipic acid was 1.02:1, a step of; the polyamide salt solution was diluted to a concentration of 10wt.% and its pH was measured to be 8.5.
(2) Under the nitrogen atmosphere, adding graphite (the addition amount is 6.5 weight percent of the total mass of 1, 5-pentanediamine and adipic acid) into the polyamide salt solution with the weight percent of 75 under the mechanical stirring, standing and soaking for 11 hours after stirring for 2 hours, and using a cell crusher to carry out ultrasonic dispersion for 3 hours with the ultrasonic power of 650W.
(3) Heating the reaction system obtained in the step (2), increasing the pressure in the reaction system to 1.65MPa, exhausting and maintaining the pressure, wherein the temperature of the reaction system is 232 ℃ when the pressure maintaining is finished, reducing the pressure to reduce the pressure in the reaction system to 0.02MPa, and maintaining the pressure for 5min, and the temperature of the reaction system is 245 ℃ when the pressure maintaining is finished. Vacuum pumping is carried out at-0.07 MPa, the temperature of the system is 265 ℃ at the end of 14min, and the melt of the modified polyamide is obtained.
(4) Granulating to obtain resin
Melting and discharging, and cooling and granulating by water; the water temperature of the cooling water is 35 ℃, the cooling time is 35min, and the modified polyamide resin is obtained.
Example 2
Preparation of antistatic Polyamide 56 resin
(1) 1, 5-pentanediamine, adipic acid and water were uniformly mixed under a nitrogen atmosphere to prepare a 75wt% polyamide salt solution. The molar ratio of 1, 5-pentanediamine to adipic acid was 1.02:1, the pH of the polyamide salt solution was measured to be 8.5 when diluted to a concentration of 10 wt.%.
(2) Under the nitrogen atmosphere and under the mechanical stirring, adding graphite and expanded graphite (the addition amounts are respectively 2.5 weight percent and 3.5 weight percent of the total mass of 1, 5-pentanediamine and adipic acid) into the polyamide salt solution with the weight percent of 75, stirring for 2 hours, standing and soaking for 11 hours, and using a cell crusher to carry out ultrasonic dispersion for 3 hours with the ultrasonic power of 600W.
(3) Heating the reaction system obtained in the step (2), increasing the pressure in the reaction system to 1.65MPa, exhausting and maintaining the pressure, wherein the temperature of the reaction system is 235 ℃ when the pressure maintaining is finished, reducing the pressure in the reaction system to 0.02MPa, maintaining the temperature for 5min, maintaining the temperature of the reaction system at 245 ℃ when the pressure maintaining is finished, vacuumizing and maintaining the temperature at-0.07 MPa for 14min, and obtaining the melt of the modified polyamide when the temperature of the reaction system is 265 ℃.
(4) Granulating to obtain resin
Melting and discharging, and cooling and granulating by water; the temperature of the cooling water is 33 ℃, and the cooling time is 35min, so as to obtain the modified polyamide resin.
Example 3
Preparation of antistatic Polyamide 56/5T resin
(1) 1, 5-pentanediamine, adipic acid, terephthalic acid and water were uniformly mixed under a nitrogen atmosphere to prepare a polyamide salt solution of 30 wt%. The molar ratio of 1, 5-pentanediamine to diacid is 1.1:1 terephthalic acid is 30 wt.% of a dibasic acid, and the pH of the polyamide salt solution is measured to be 9.2 when diluted to a concentration of 10 wt.%.
(2) Under the nitrogen atmosphere and under the mechanical stirring, adding graphene (the addition amount is 1wt% of the total mass of 1, 5-pentanediamine and diacid) into the polyamide salt solution with the weight percent of 30, stirring for 2 hours, standing and soaking for 12 hours, and using a cell crusher to carry out ultrasonic dispersion for 4 hours, wherein the ultrasonic power is 650W.
(3) Heating the reaction system obtained in the step (2), wherein the pressure in the reaction system is increased to 2.2MPa, exhausting and maintaining the pressure, the temperature of the reaction system is 265 ℃ when the pressure maintaining is finished, then reducing the pressure to reduce the pressure in the reaction system to 0.15MPa, maintaining the temperature for 20min, maintaining the temperature of the reaction system at 320 ℃ when the pressure maintaining is finished, vacuumizing and maintaining the temperature at-0.09 MPa for 13min, and maintaining the temperature of the reaction system at 330 ℃ when the pressure maintaining is finished, thus obtaining the melt of the modified polyamide.
(4) Granulating to obtain resin
Melting and discharging, and cooling and granulating by water; the water temperature of the cooling water is 10 ℃, the cooling time is 35min, and the modified polyamide resin is obtained.
Example 4
Preparation of antistatic Polyamide 56/5T resin
The conductive material in the step (2) is graphite, and the addition amount is 1wt% of the total mass of the 1, 5-pentanediamine and the dibasic acid; the other components are the same as in example 4.
Example 5
Preparation of antistatic Polyamide 510 resin
(1) 1, 5-pentanediamine, decanedioic acid and water were uniformly mixed under a nitrogen atmosphere to prepare a 41wt% polyamide salt solution. Wherein, the mol ratio of the 1, 5-pentanediamine to the sebacic acid is 1.03:1, the pH of the polyamide salt solution was measured to be 8.3 when it was diluted to a concentration of 10 wt.%.
(2) Under the nitrogen atmosphere and under the mechanical stirring, graphene oxide (the addition amount is 5.5 weight percent of the total mass of 1, 5-pentanediamine and sebacic acid) is added into the 41 weight percent polyamide salt solution, and after stirring for 2 hours, the mixture is stood and infiltrated for 8 hours, and is dispersed for 1 hour by using a cell breaker in an ultrasonic way, wherein the ultrasonic power is 300W.
(3) Heating the reaction system obtained in the step (2), wherein the pressure in the reaction system is increased to 1.5MPa, the temperature of the reaction system is 243 ℃ when the pressure maintaining is finished, then reducing the pressure to reduce the pressure in the reaction system to 0.1MPa, keeping the temperature for 13min, keeping the temperature of the reaction system at 265 ℃ when the pressure maintaining is finished, vacuumizing and keeping the temperature at-0.085 MPa for 21min, and keeping the temperature of the reaction system at 285 ℃ when the pressure maintaining is finished, thus obtaining the melt of the modified polyamide.
(4) Granulating to obtain resin
Melting and discharging, and cooling and granulating by water; the water temperature of the cooling water is 23 ℃, and the cooling time is 35min, so as to obtain the modified polyamide resin.
Example 6
Preparation of antistatic Polyamide 512 resin
(1) Under the nitrogen atmosphere, 1, 5-pentanediamine, lauryldiacid and water are uniformly mixed to prepare 45wt percent polyamide salt solution. The molar ratio of 1, 5-pentanediamine to lauryldiacid is 1.06:1, the pH of the polyamide salt solution was measured to be 8.71 when it was diluted to a concentration of 10 wt.%.
(2) Under the nitrogen atmosphere and under the mechanical stirring, adding graphite oxide (the addition amount is 5.7 weight percent of the total mass of 1, 5-pentanediamine and lauryldiacid) into the 45 weight percent polyamide salt solution, stirring for 2 hours, standing and soaking for 8-12 hours, and using a cell crusher to ultrasonically disperse for 1.5 hours, wherein the ultrasonic power is 370W.
(3) Heating the reaction system obtained in the step (2), increasing the pressure in the reaction system to 1.65MPa, exhausting and maintaining the pressure, reducing the pressure to reduce the pressure in the reaction system to 0.08MPa when the pressure is maintained, maintaining the temperature for 15min, maintaining the temperature of the reaction system at 267 ℃ when the pressure is maintained at minus 0.083MPa, maintaining the pressure for 19min, and maintaining the temperature of the reaction system at 281 ℃ when the pressure is maintained, thus obtaining the melt of the modified polyamide.
(4) Granulating to obtain resin
Melting and discharging, and cooling and granulating by water; the temperature of the cooling water is 27 ℃, and the cooling time is 35min, so as to obtain the modified polyamide resin.
Example 7
Preparation of antistatic Polyamide 516 resin
(1) Under the nitrogen atmosphere, 1, 5-pentanediamine, hexadecanedioic acid and water are uniformly mixed to prepare 47wt% of polyamide salt solution. The molar ratio of 1, 5-pentanediamine to hexadecanediacid is 1.04:1, the pH of the polyamide salt solution was measured to be 8.3 when it was diluted to a concentration of 10 wt.%.
(2) Under the nitrogen atmosphere and under the mechanical stirring, adding graphene (the addition amount is 1.5 weight percent of the total mass of 1, 5-pentanediamine and hexadecane diacid) into the 47 weight percent polyamide salt solution, stirring for 2 hours, standing and infiltrating for 12 hours, and using a cell crusher to carry out ultrasonic dispersion for 4 hours with the ultrasonic power of 600W.
(3) Heating the reaction system obtained in the step (2), increasing the pressure in the reaction system to 1.55MPa, exhausting and maintaining the pressure, wherein the temperature of the reaction system is 236 ℃ when the pressure maintaining is finished, reducing the pressure in the reaction system to 0.06MPa, maintaining the temperature for 30min, maintaining the temperature of the reaction system at 247 ℃ when the pressure maintaining is finished, vacuumizing and maintaining the temperature at-0.06 MPa for 42min, and maintaining the temperature of the reaction system at 260 ℃ when the pressure maintaining is finished, so as to obtain the melt of the modified polyamide.
(4) Granulating to obtain resin
Melting and discharging, and cooling and granulating by water; the water temperature of the cooling water is 30 ℃, the cooling time is 35min, and the modified polyamide resin is obtained.
Example 8
Preparation of antistatic Polyamide 66 resin
(1) 1, 6-hexamethylenediamine, adipic acid and water were uniformly mixed under a nitrogen atmosphere to prepare a 50wt% polyamide salt solution. The molar ratio of 1, 6-hexamethylenediamine to adipic acid is 1.01:1, the pH of the polyamide salt solution was measured to be 8.1 when it was diluted to a concentration of 10 wt.%.
(2) Under the nitrogen atmosphere and under the mechanical stirring, the expanded graphite (the addition amount is 3.5 weight percent of the total mass of 1, 6-hexamethylenediamine and adipic acid) is added into the 50 weight percent polyamide salt solution, and after stirring for 2 hours, the mixture is kept stand and soaked for 9.5 hours, and is dispersed for 1.5 hours by using a cell breaker in an ultrasonic way, and the ultrasonic power is 570W.
(3) Heating the reaction system obtained in the step (2), increasing the pressure in the reaction system to 1.7MPa, exhausting and maintaining the pressure, wherein the temperature of the reaction system is 238 ℃ when the pressure maintaining is finished, reducing the pressure in the reaction system to 0.06MPa, maintaining the temperature for 30min, maintaining the temperature of the reaction system at 267 ℃ when the pressure maintaining is finished, vacuumizing and maintaining the temperature at-0.06 MPa for 8min, and maintaining the temperature of the reaction system at 280 ℃ when the pressure maintaining is finished, so as to obtain the melt of the modified polyamide.
(4) Granulating to obtain resin
Melting and discharging, and cooling and granulating by water; the temperature of the cooling water is 18 ℃, the cooling time is 35min, and the modified polyamide resin is obtained.
Example 9
Preparation of antistatic Polyamide 56/5T resin
Step (1) was carried out by adjusting the pH of the polyamide salt solution with 1mol/L hydrochloric acid so that the pH of the resulting 30wt% polyamide salt solution was 6.8 when diluted to a concentration of 10wt%, and step (2) was carried out by adjusting the pH of the polyamide salt solution to 30wt%, all other than in example 3.
Example 10
The stirring in the step (2) for 2 hours did not have a process of static infiltration for 12 hours, and the other steps are the same as in example 3.
Comparative example 1
Preparation of Polyamide 56 resin
(1) 1, 5-pentanediamine, adipic acid and water are uniformly mixed under the nitrogen atmosphere to prepare a 75wt% polyamide salt solution, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1.02:1, the pH of the polyamide salt solution was measured to be 8.5 when it was diluted to a concentration of 10 wt.%.
(2) Heating the polyamide salt solution, increasing the pressure in a reaction system to 1.65MPa, exhausting and maintaining the pressure, wherein the temperature of the reaction system is 232 ℃ when the pressure maintaining is finished, reducing the pressure in the reaction system to 0.02MPa, maintaining the temperature for 5min, maintaining the temperature of the reaction system at 245 ℃ when the pressure maintaining is finished, vacuumizing and maintaining the temperature at-0.07 MPa for 14min, and obtaining the melt of the polyamide when the temperature of the reaction system is 265 ℃.
(3) Granulating to obtain resin
Melting and discharging, and cooling and granulating by water; the temperature of the cooling water is 35 ℃, the cooling time is 35min, and the polyamide resin is obtained.
Comparative example 2
Preparation of Polyamide 56/5T resin
(1) 1, 5-pentanediamine, adipic acid, terephthalic acid and water were uniformly mixed under a nitrogen atmosphere to prepare a polyamide salt solution of 30 wt%. The molar ratio of 1, 5-pentanediamine to diacid is 1.1:1 terephthalic acid is 30 wt.% of a dibasic acid, and the pH of the polyamide salt solution is measured to be 9.2 when diluted to a concentration of 10 wt.%.
(2) Heating the reaction system obtained in the step (2), increasing the pressure in the reaction system to 2.2MPa, exhausting and maintaining the pressure, wherein the temperature of the reaction system is 265 ℃ when the pressure maintaining is finished, reducing the pressure in the reaction system to 0.15MPa, maintaining the pressure for 2-30min, maintaining the temperature of the reaction system at 320 ℃ when the pressure is finished, vacuumizing and maintaining the temperature at-0.09 MPa, maintaining the pressure for 13min, and maintaining the temperature of the reaction system at 330 ℃ when the pressure is finished, thus obtaining the melt of the polyamide.
(3) Granulating to obtain resin
Melting and discharging, and cooling and granulating by water; the water temperature of the cooling water is 10 ℃, the cooling time is 35min, and the polyamide resin.
Comparative example 3
Preparation of Polyamide 510 resin
(1) 1, 5-pentanediamine, decanedioic acid and water were uniformly mixed under a nitrogen atmosphere to prepare a 41wt% polyamide salt solution. The molar ratio of 1, 5-pentanediamine to sebacic acid was 1.03:1, the pH of the polyamide salt solution was measured to be 8.3 when it was diluted to a concentration of 10 wt.%.
(2) Heating the reaction system obtained in the step (2), increasing the pressure in the reaction system to 1.5MPa, exhausting and maintaining the pressure, wherein the temperature of the reaction system is 243 ℃ when the pressure maintaining is finished, reducing the pressure in the reaction system to 0.1MPa, maintaining the pressure for 13min, maintaining the temperature of the reaction system at 265 ℃ when the pressure is finished, vacuumizing and maintaining the temperature at-0.085 MPa, maintaining the pressure for 21min, and maintaining the temperature of the reaction system at 285 ℃ when the pressure is finished, so as to obtain the melt of the polyamide.
(3) Granulating to obtain resin
Melting and discharging, and cooling and granulating by water; the cooling water temperature is 23 ℃, the cooling time is 35min, and the polyamide resin is obtained.
Comparative example 4
Preparation of Polyamide 512 resin
(1) Under the nitrogen atmosphere, 1, 5-pentanediamine, lauryldiacid and water are uniformly mixed to prepare 45wt percent polyamide salt solution. The molar ratio of 1, 5-pentanediamine to lauryldiacid is 1.06:1, the pH of the polyamide salt solution was measured to be 8.71 when it was diluted to a concentration of 10 wt.%.
(2) Heating the reaction system obtained in the step (2), increasing the pressure in the reaction system to 1.65MPa, exhausting and maintaining the pressure, reducing the pressure to reduce the pressure in the reaction system to 0.08MPa when the pressure is maintained, maintaining the temperature for 15min, maintaining the temperature of the reaction system at 267 ℃ when the pressure is maintained at minus 0.083MPa, maintaining the pressure for 19min, and maintaining the temperature of the reaction system at 281 ℃ when the pressure is maintained, thus obtaining the melt of the polyamide.
(3) Granulating to obtain resin
Melting and discharging, and cooling and granulating by water; the temperature of the cooling water is 27 ℃, and the cooling time is 35min, so as to obtain the polyamide resin.
Comparative example 5
Preparation of Polyamide 516 resin
(1) Under the nitrogen atmosphere, 1, 5-pentanediamine, hexadecanedioic acid and water are uniformly mixed to prepare 47wt% of polyamide salt solution. The molar ratio of 1, 5-pentanediamine to hexadecanediacid is 1.04:1, the pH of the polyamide salt solution was measured to be 8.3 when it was diluted to a concentration of 10 wt.%.
(2) Heating the reaction system obtained in the step (2), increasing the pressure in the reaction system to 1.55MPa, exhausting and maintaining the pressure, wherein the temperature of the reaction system is 236 ℃ when the pressure maintaining is finished, reducing the pressure in the reaction system to 0.06MPa, maintaining the temperature for 30min, maintaining the temperature of the reaction system at 247 ℃ when the pressure maintaining is finished, vacuumizing and maintaining the temperature at-0.06 MPa for 42min, and maintaining the temperature of the reaction system at 260 ℃ when the pressure maintaining is finished, so as to obtain the melt of the polyamide.
(3) Granulating to obtain resin
Melting and discharging, and cooling and granulating by water; the temperature of the cooling water is 30 ℃, the cooling time is 35min, and the polyamide resin is obtained.
Comparative example 6
Preparation of Polyamide 66 resin
(1) 1, 6-hexamethylenediamine, adipic acid and water were uniformly mixed under a nitrogen atmosphere to prepare a 50wt% polyamide salt solution. The molar ratio of 1, 6-hexamethylenediamine to adipic acid is 1.01:1, the pH of the polyamide salt solution was measured to be 8.1 when it was diluted to a concentration of 10 wt.%.
(2) Heating the reaction system obtained in the step (2), increasing the pressure in the reaction system to 1.7MPa, exhausting and maintaining the pressure, wherein the temperature of the reaction system is 238 ℃ when the pressure maintaining is finished, reducing the pressure in the reaction system to 0.06MPa, maintaining the temperature for 30min, maintaining the temperature of the reaction system at 267 ℃ when the pressure maintaining is finished, vacuumizing and maintaining the temperature at-0.06 MPa for 8min, and maintaining the temperature of the reaction system at 280 ℃ when the pressure maintaining is finished, so as to obtain the melt of the modified polyamide.
(3) Granulating to obtain resin
Melting and discharging, and cooling and granulating by water; the temperature of the cooling water is 18 ℃, the cooling time is 35min, and the modified polyamide resin is obtained.
Comparative example 7
Graphite micropowder (the addition amount is 6.5wt% of the total mass of the polyamide resin) was added to the polyamide resin obtained in comparative example 1, and a blend modified polyamide 56 resin was produced by extrusion molding.
Comparative example 8
Graphite micropowder (the addition amount is 21wt% of the total mass of the polyamide) was added to the polyamide resin obtained in comparative example 1, and a blend modified polyamide 56 resin was produced by extrusion molding.
Effect examples
1. Method for detecting relative viscosity eta r
Concentrated sulfuric acid process with Ubbelohde viscometer: the dried resins of the modified polyamides obtained in examples 1 to 10 and the polyamide or blended modified polyamide resin samples obtained in comparative examples 1 to 8 were each accurately weighed at 0.5.+ -. 0.0002g, and 50mL of concentrated sulfuric acid (98%) was added for dissolution to obtain a sample solution, and the flow-through time t of the concentrated sulfuric acid (98%) was measured and recorded in a constant temperature water bath at 25 ℃ 0 And the sample solution flow time t, the results are shown in Table 1.
The relative viscosity number calculation formula:
relative viscosity ηr=t/t 0
Wherein: t: sample solution flow time;
t 0 : concentrated sulfuric acid (98%) was passed over time.
2. Method for detecting melting point (Tm)
The modified polyamide resins obtained in examples 1 to 10 and the polyamide or blended modified polyamide resins obtained in comparative examples 1 to 8 were tested for melting point by means of a Perkin Elmer DSC-6 analyzer under a nitrogen atmosphere at a flow rate of 40mL/min. The melting point was measured by heating to 310℃at 10℃per minute, maintaining at 290℃for 3 minutes, cooling to 30℃at 10℃per minute, and heating to 310℃at 10℃per minute, and the results are shown in Table 1.
3. Volume resistivity detection method
The volume resistivity of the resins of the modified polyamides obtained in examples 1 to 10 and the resin samples of the polyamides obtained in comparative examples 1 to 8 or blended modified polyamides were measured according to the GB/T31838-2019 method, and the results are shown in Table 1.
4. Method for detecting tensile strength and elongation at break of resin
The tensile strength and elongation at break of the resins of the modified polyamides obtained in examples 1 to 10 and the resin samples of the polyamides obtained in comparative examples 1 to 8 or blended modified polyamides were measured according to GB/T1040.2-2006 method; detection conditions: 23 ℃,50% humidity, for 24 hours, the results are shown in table 1.
5. Method for detecting bending strength of resin
The flexural strength of the resins of the modified polyamides obtained in examples 1 to 10 and the resin samples of the polyamides obtained in comparative examples 1 to 8 or blended modified polyamides were measured according to the GB/T9341-2008 method, and the results are shown in Table 1.
6. Method for detecting notch impact strength of resin cantilever beam
The notched Izod impact strength of the resins of the modified polyamides obtained in examples 1 to 10 and the resins of the polyamides obtained in comparative examples 1 to 8 or the resin samples blended with the modified polyamides were measured according to the GB/T1043-2018 method and the results are shown in Table 1.
Table 1 table of performance data for examples and comparative examples
The data in Table 1 shows that the modified polyamide prepared by the invention has similar melting point, relative viscosity, tensile strength, elongation at break, bending strength and notch impact strength as the unmodified polyamide with the same composition, and has good mechanical properties and processability; and volume resistivity of the order of 10 4～6 The range is obviously lower than that of an unmodified sample, which shows that the modified polyamide prepared by the method has excellent antistatic effect, wherein the antistatic effect of the modified polyamide obtained by taking the graphene or graphene oxide of the examples 3, 5 and 7 as the conductive material is better. Example 9 the pH of the polyamide salt solution of step (1) alone at a concentration of 10wt.% became smaller compared to example 3, and the antistatic effect of the resulting modified polyamide was relatively poorer than that of example 3. Example 10 compared to example 3, the modified polyamide produced by adding the conductive material of step (2) to the polyamide salt solution and stirring without the infiltration process had relatively poorer antistatic effect than example 3.
Comparative example 7 shows that the prior art is incorporated by physical extrusion blending as in the present inventionThe resistivity of the prepared blended modified polyamide is obviously higher than that of the invention 10 when the conductive material is in proportion 4～6 An order of magnitude; comparative example 8 shows that when the volume resistivity of the blend is to be of the same order of magnitude as the volume resistivity of the present invention by physical extrusion, a large amount of conductive filler (more than 20%) is required to be added, and the mechanical properties of the material, such as tensile strength, elongation at break, flexural strength and notched impact strength, are significantly reduced. Comparative examples 1 to 6 show that the modified polyamide prepared by the invention has better antistatic effect, and meanwhile, the mechanical property of the modified polyamide is basically equivalent to that of the polyamide without conductive materials.
Claims (10)
1. A modified polyamide comprising a polyamide matrix and a conductive material distributed in the polyamide matrix, wherein the mass ratio of the conductive material to a polymerization raw material of the polyamide matrix is (0.5-15): 100, and the modified polyamide has a volume resistivity of 1X 10 4 ～9×10 7 Ω·m。
2. The modified polyamide of claim 1, wherein the conductive material is a carbon-based conductive material, preferably one or more of conductive carbon black, graphite, expanded graphite, graphite oxide, graphene oxide, and graphene;
and/or the polyamide matrix is one or more of nylon 6, nylon 66, nylon 12, nylon 46, nylon 610, nylon 612, nylon l010, polyamide 5X/5T and polyamide 5X/5I;
among them, polyamide 5X is preferably a polyamide obtained by polycondensation of 1, 5-pentanediamine and an aliphatic dibasic acid having a carbon number of X; preferably, X is any integer from 4 to 18, more preferably 4, 6, 10, 12 or 16;
the polyamide 5X/5T is preferably a polyamide obtained by polycondensation of 1, 5-pentanediamine, an aliphatic dibasic acid having X carbon atoms and terephthalic acid; preferably, X is any integer from 4 to 18, more preferably 6;
the polyamide 5X/5I is preferably a polyamide obtained by polycondensation of 1, 5-pentanediamine, an aliphatic dibasic acid having X carbon atoms and isophthalic acid; preferably, X is any integer from 4 to 18, more preferably 6.
3. The modified polyamide of claim 1 wherein the polymeric raw materials comprise a diamine and a diacid;
wherein the diamine is preferably any one of terminal diamine with 1-10 carbon atoms, more preferably butanediamine, hexanediamine or 1, 5-pentanediamine;
the diacid is preferably an aliphatic diacid, a mixture of an aliphatic diacid and terephthalic acid, or a mixture of an aliphatic diacid and isophthalic acid; the aliphatic dibasic acid has preferably any integer of 4 to 18 carbon atoms, more preferably 4, 6, 10, 12 or 16 carbon atoms;
the molar ratio of the diamine to the diacid is preferably (0.9-1.2): 1, more preferably (1-1.2): 1, more preferably 1.01:1, 1.02:1, 1.03:1, 1.04:1, 1.06:1 or 1.07:1;
and/or the mass ratio of the conductive material to the raw material of the polyamide matrix is (1-10): 100, preferably (1.5-6): 100, more preferably 3.5:100, 5.5:100, 5.7:100, 6:100 or 6.5:100.
4. The modified polyamide of claim 1 wherein said volume resistivity is 1 x 10 4 ～9×10 6 Omega.m, preferably 7.8X10 4 ～8.4×10 6 Ω·m；
And/or the tensile strength of the modified polyamide is 51-94 MPa;
and/or the elongation at break of the modified polyamide is 3.8-243%;
and/or the bending strength of the modified polyamide is 95-107 MPa;
and/or the modified polyamide has a notched impact strength of 5.1 to 6.2KJ/m 2 ；
And/or the melting point of the modified polyamide is 194-310 ℃, preferably 194-290 ℃, more preferably 194-268 ℃;
and/or the relative viscosity of the modified polyamide is 2.33-2.51.
5. A process for producing a modified polyamide as claimed in any one of claims 1 to 4, comprising the steps of: the mixture comprising polyamide salt and the conductive material is subjected to polymerization reaction; the polyamide salt is the product of the reaction of the polymeric raw materials in water.
6. The process for producing a modified polyamide as claimed in claim 5, wherein the concentration of the polyamide salt solution is 30 to 90% by weight, preferably 50 to 75% by weight;
and/or the pH of the polyamide salt solution when diluted to a concentration of 10wt% is 6.5 or more, preferably 6.3 to 9.2, more preferably 7.2 to 9.2, still more preferably 8.1, 8.3, 8.5 or 8.8;
and/or the preparation method of the mixture is any one of the following modes:
mode one: the conductive material, the polymerization raw material and water are mixed and reacted;
mode two: mixing the polymerization raw material with water, reacting to generate a polyamide salt solution, and then mixing with the conductive material;
and/or, the mixture is further subjected to a step of infiltration before the polymerization reaction is carried out; the infiltration is preferably static; the time of the infiltration is preferably 6 to 20 hours, more preferably 8 to 12 hours, still more preferably 11 hours; the post-infiltration, pre-polymerization step preferably further comprises a dispersing step, preferably ultrasonic dispersion; the time of the ultrasonic dispersion is preferably 1 to 5 hours, more preferably 3 hours; the ultrasonic power in the ultrasonic dispersion is preferably 500-800W, more preferably 650W; the ultrasonic dispersing device is preferably a cell breaker.
7. The process for producing a modified polyamide as claimed in claim 5, wherein the polymerization is a solution polymerization, preferably by the following procedure: performing pressure maintaining reaction under the initial pressure, reducing the pressure to the intermediate pressure, performing pressure maintaining reaction, vacuumizing, and performing pressure maintaining reaction;
wherein the initial pressure is preferably 0.5-3MPa, more preferably 0.8-2.2 MPa, even more preferably 1.5MPa, 1.55MPa, 1.65MPa, 1.7MPa or 2.1MPa, wherein the pressures are gauge pressures;
the temperature at the end of the holding at the initial pressure is preferably 200 to 300 ℃, more preferably 232 to 265 ℃, still more preferably 235 ℃, 238 ℃, 241 ℃ or 243 ℃;
the intermediate pressure is preferably 0 to 0.2MPa, more preferably 0 to 0.15MPa, even more preferably 0.02MPa, 0.06MPa, 0.08MPa or 0.1MPa, wherein the pressures are gauge pressures;
the pressure maintaining reaction time under the intermediate pressure is preferably 2-30min, more preferably 5min, 8min or 13min;
the temperature at the end of the pressure maintaining reaction at the intermediate pressure is preferably 200 to 350 ℃, more preferably 245 to 320 ℃, still more preferably 247, 265, 267 or 307 ℃;
the pressure after vacuum pumping is preferably-0.005 to-0.12 MPa, more preferably-0.01 to-0.09 MPa, more preferably-0.07 MPa, -0.085MPa, -0.083MPa or-0.06 MPa;
the pressure maintaining reaction time after the vacuumizing is preferably 8-42 min, more preferably 8, 13, 14 or 15min;
the temperature at the end of the pressure maintaining reaction after the vacuum pumping is preferably 260 to 330 ℃, more preferably 265 ℃, 281 ℃, 285 ℃, 308 ℃, 323 ℃ or 330 ℃.
8. A modified polyamide obtained by the production process according to any one of claims 5 to 7.
9. Use of a modified polyamide according to any one of claims 1 to 4, 8 in antistatic materials.
10. A modified polyamide article obtained by molding the modified polyamide according to any one of claims 1 to 4 and 8.
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