RU2641134C1 - Electrically conductive metal-filled polymer compound for 3d-printing (versions) - Google Patents

Abstract

FIELD: electricity.

SUBSTANCE: electrically conductive polymer compound as a polymer base contains a polymer of styrene-butadiene-styrene (SBS) in the amount of 10 wt %, as a conductive metal filler - solder Sn-63 or lead in amount of 40 wt %, and as a plasticiser - oil OP-6s in amount of 50 wt %. Version of compound as polymer base contains the SBS in the amount of 10-20 wt %, as conductive metal filler - copper or aluminium in the amount of 30-40 wt %, and as a plasticiser - oil OP-6s in the amount of 50 wt %.

EFFECT: increase in electrical conductivity and melt flow index for polymer composites intended for 3D printing.

2 cl, 1 tbl, 16 ex

Description

The invention relates to the field of producing electrically conductive polymer compositions used for the manufacture of conductive materials intended for 3D printing.

The invention can be applied to the production of 3D-printed electrically conductive materials, such as mechanosensors, capacitive detection devices, automated dynamic mechanisms.

Known conductive polymer compositions based on copper and thermoplastics or epoxy resins used for the manufacture of electronic objects [Conductive polymer composites. Patent US20080272344 A1, No. 12/077.812].

The disadvantage of this polymer composition is its low electrical conductivity and fluidity due to the use of filled polymer.

Closest to the proposed electrically conductive composition are electrically conductive compositions [Abdullin M.I., Basyrov A.A., Nikolaev A.V. Metal-polymer compositions for 3D printing // Universum: Chemistry and Biology: Electron. scientific journal 2015. No. 11 (18).] Based on polyvinyl acetate grade M10 and a metal filler (lead grade PS, nickel grade A-2, copper grade PMU, aluminum grade PAD-4), of the following composition, wt%:

1. Polyvinyl acetate grade M10 - lead grade PS with a degree of filling of 0-50%;

2. Polyvinyl acetate grade M10 - nickel grade A-2 with a degree of filling of 0-70%

3. Polyvinyl acetate grade M10 - PMU grade copper with a degree of filling of 0-70%;

4. Polyvinyl acetate grade M10 - aluminum grade PAD-4 with a degree of filling of 0-70%

The disadvantage of these electrically conductive compositions is the low electrical conductivity (less than 1⋅10 ^-4 (Ohm × mm ² / cm) ^-1 ), which does not allow the manufacture of conductive three-dimensional objects based on them using 3D printing.

The technical result of the invention is to obtain polymer compositions with high electrical conductivity and manufacturability, designed for 3D printing.

The indicated technical result is achieved by the fact that SBS-styrene-butadiene-styrene copolymer is used as the polymer base of the electrically conductive composition, and metal fillers: POS-63, lead, aluminum, copper are used as conductive powders. The proposed composition further comprises a plasticizer - oil PN-6Sh.

Conductive powder POS-63 is a tin-lead alloy. Composition: tin - 63%; lead - 27% (TU 48-13-39-89). Oil PN-6Sh (TU 38.1011217-89) - an oil plasticizer, is a concentrate of aromatic hydrocarbons. It is obtained by compounding the extracts of selective (phenolic) purification of oil fractions of oil.

The use of SBS in the composition of the conductive composition can significantly increase the conductivity and melt flow rate of the conductive polymer compositions in comparison with the prototype.

An electrically conductive polymer composition is prepared as follows.

20-40 wt% metal filler is charged into the reactor; 10-30 wt% SBS; 50 wt% oil PN-6Sh. The components are mixed in a metal mixer equipped with a mechanical stirrer for 12 minutes at a stirring speed of 440 min ^-1 .

The powdery composition obtained is loaded into a laboratory single screw extruder (D / L = 15 cm, coil depth 16.5 mm, crest width 20 mm) and an extrudate is obtained at a material cylinder temperature of 150 ° C and a screw rotation speed of 30 min ^-1 .

The electrical conductivity of the thus prepared polymer compositions is measured on cylindrical samples with a length of about 20 mm and a diameter of 4 mm by contact method. The melt flow rate of polymer compositions is measured on an IIRT-AM extrusion plastograph. The value of electrical conductivity and PTR of polymer compositions is determined according to GOST 11645-73.

The invention is illustrated by the following examples.

Example 1

Into the mixer load 30 wt% SBS; 20 wt% POS-63; 50 wt% oil PN-6Sh. The composition is mixed in a mixer for 12 min at a stirring speed of 440 min ^-1 . The resulting powdery composition is granulated on a laboratory single screw extruder at a temperature of 150 ° C. The resulting polymer composition does not have electrical conductivity, melt flow rate of 3.7 g / 10 min.

Example 2

In the conditions of example 1 at the next load of the components, wt%: SBS - 20; POS-63 - 30; PN-6Sh oil - 50. The obtained polymer composition does not have electrical conductivity, melt flow rate of 0.5 g / 10 min.

Example 3

In the conditions of example 1 at the next load of the components, wt%: SBS - 10; POS-63 - 40; PN-6Sh oil - 50. The electrical conductivity of the polymer composition is 1.2 × 10 ^-2 (Ohm × mm ² / cm) ^-1 , the melt flow rate is 0.2 g / 10 min.

Example 4

In the conditions of example 1 at the next load of the components, wt%: SBS - 5; POS-63 - 45; PN-6Sh oil - 50. The electrical conductivity of the polymer composition is 0.20 (Ohm × mm ² / cm) ^-1 , the melt of the polymer composition does not show fluidity.

Example 5

In the conditions of example 1 at the next load of the components, wt%: SBS - 30; lead - 20; PN-6Sh oil - 50. The resulting polymer composition does not have electrical conductivity, melt flow rate of 1.53 g / 10 min.

Example 6

In the conditions of example 1 at the next load of the components, wt%: SBS - 20, lead - 30; PN-6Sh oil - 50. The resulting polymer composition does not have electrical conductivity, melt flow rate of 0.3 g / 10 min.

Example 7

In the conditions of example 1 at the next load of the components, wt%: SBS - 10, lead - 40; PN-6Sh oil - 50. The electrical conductivity of the polymer composition is 2.2 × 10 ^-2 (Ohm × mm ² / cm) ^-1 , the melt flow rate is 0.1 g / 10 min.

Example 8

In the conditions of example 1 at the next load of the components, wt%: SBS - 5, lead - 45; PN-6Sh oil - 50. The electrical conductivity of the polymer composition is 0.21 (Ohm × mm ² / cm) ^-1 , the melt of the polymer composition does not show fluidity.

Example 9

In the conditions of example 1 at the next load of the components, wt%: SBS - 30; copper - 20; PN-6Sh oil - 50. The resulting polymer composition does not have electrical conductivity, melt flow rate of 2.8 g / 10 min.

Example 10

In the conditions of example 1 at the next load of the components, wt%: SBS - 20; copper - 30; PN-6Sh oil - 50. The electrical conductivity of the polymer composition is 1.7 × 10 ^-2 (Ohm × mm ² / cm) ^-1 , the melt flow rate is 0.9 g / 10 min.

Example 11

In the conditions of example 1 at the next load of the components, wt%: SBS - 10; copper - 40; PN-6Sh oil - 50. The electrical conductivity of the polymer composition is 6.5 × 10 ^-2 (Ohm × mm ² / cm) ^-1 , the melt flow rate is 0.3 g / 10 min.

Example 12

In the conditions of example 1 at the next load of the components, wt%: SBS - 5; copper - 45; PN-6Sh oil - 50. The electrical conductivity of the polymer composition is 0.11 (Ohm × mm ² / cm) ^-1 , the melt of the polymer composition does not show fluidity.

Example 13

In the conditions of example 1 at the next load of the components, wt%: SBS - 30; aluminum - 20; PN-6Sh oil - 50. The resulting polymer composition does not have electrical conductivity, melt flow rate of 3 g / 10 min.

Example 14

In the conditions of example 1 at the next load of the components, wt%: SBS - 20; aluminum - 30; PN-6Sh oil - 50. The electrical conductivity of the polymer composition is 1.1 × 10 ^-2 (Ohm × mm ² / cm) ^-1 , the melt flow rate is 0.4 g / 10 min.

Example 15

In the conditions of example 1 at the next load of the components, wt%: SBS - 10; aluminum - 40; PN-6Sh oil - 50. The electrical conductivity of the polymer composition is 3.6 × 10 ^-2 (Ohm × mm ² / cm) ^-1 , the melt flow rate is 0.1 g / 10 min.

Example 16

In the conditions of example 1 at the next load of the components, wt%: SBS - 5; aluminum - 45; PN-6Sh oil - 50. The electrical conductivity of the polymer composition is 0.1 (Ohm × mm ² / cm) ^-1 , the melt of the polymer composition does not show fluidity.

Thus, the use of SBS as the polymer base allows one to obtain polymer compositions with increased electrical conductivity and manufacturability, intended for the manufacture of three-dimensional objects by 3D printing, which involves the application of an electrically conductive polymer layer in the form of a melt.

The use of PN-6Sh oil as a plasticizer increases the elasticity of metal-filled compositions during their processing and operation.

Claims (4)

1. An electrically conductive metal-filled polymer composition for 3D printing, consisting of a polymer base, a conductive filler, characterized in that the composition further comprises a plasticizer, while the polymer base contains a styrene-butadiene-styrene polymer (SBS), as a conductive filler contains metal filler - solder grade POS-63 or lead, and as a plasticizer - oil PN-6Sh in the following ratio, wt. %: SBS polymer 10 Filler 40 Plasticizer fifty 2. An electrically conductive metal-filled polymer composition for 3D printing, consisting of a polymer base, a conductive filler, characterized in that the composition further comprises a plasticizer, while the polymer base contains a styrene-butadiene-styrene polymer (SBS), as a conductive filler contains the metal filler is copper or aluminum, and PN-6Sh oil is used as a plasticizer in the following ratio, wt. %: SBS polymer 10-20 Filler 30-40 Plasticizer fifty