RU2641921C2 - Electrically conductive metal-filled polymer compound for 3d-printing (versions) - Google Patents

Abstract

FIELD: electricity.

SUBSTANCE: electrically conductive polymer composition contains syndiotactic 1,2-polybutadiene (1,2-SPB) in the amount of 60-50 wt % as a polymeric base and a solder of Sn-63 or lead is the rest as a conductive metal filler. The version of composition contains syndiotactic 1,2-SPB in the amount of 70-50 wt % by as polymeric base, and as a conductive metallic filler: copper or aluminium for the rest.

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

2 cl, 1 tbl, 20 ex

Description

Electrically conductive metal-filled polymer compositions for 3D printing (options)

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), 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 on their basis by 3D printing.

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

The specified technical result is achieved by the fact that syndiotactic 1,2-polybutadiene (1,2-SPB) is used as the polymer base of the electrically conductive composition, conductive powders: POS-63, lead, aluminum, copper are used as a metal filler.

Conductive powder POS-63 is a tin-lead alloy. Composition: tin - 63%; lead - 27% (TU 48-13-39-89). The use of 1,2-SPB in the composition of the electrically conductive composition can significantly increase the conductivity and melt flow rate of the electrically conductive polymer compositions in comparison with the prototype.

An electrically conductive polymer composition is prepared as follows.

20-60 wt. % metal filler, 40-80 wt. % 1,2-SPB. 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

In the mixer load 80 wt. % 1,2-SPB; 20 wt. % POS-63. 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, the melt flow rate of 15.2 g / 10 min.

Example 2

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 70; POS-63 - 30. The obtained polymer composition does not have electrical conductivity, melt flow rate of 9.1 g / 10 min.

Example 3

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 60; POS-63 - 40. The electrical conductivity of the polymer composition is 1 × 10 ^-4 (Ohm × mm ² / cm) ^-1 , the melt flow rate is 3.8 g / 10 min.

Example 4

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 50; POS-63 - 50. The electrical conductivity of the polymer composition is 1 × 10 ^-3 (Ohm × mm ² / cm) ^-1 , the melt flow index is 1.6 g / 10 min.

Example 5

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 40; POS-63 - 60. The electrical conductivity of the polymer composition is 3 × 10 ^-3 (Ohm × mm ² / cm) ^-1 , the melt of the polymer composition does not show fluidity.

Example 6

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 80; lead - 20. The resulting polymer composition does not have electrical conductivity, melt flow rate of 12.2 g / 10 min.

Example 7

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 70; lead - 30. The resulting polymer composition does not have electrical conductivity, melt flow rate of 8.0 g / 10 min.

Example 8

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 60; lead - 40. The electrical conductivity of the polymer composition is 1 × 10 ^-4 (Ohm × mm ² / cm) ^-1 , the melt flow rate of 2.0 g / 10 min

Example 9

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 50; lead - 50. The conductivity of the polymer composition is 1⋅10 ^-3 (ohms × ² mm / cm) ^-1, a melt index of 0.7 g / 10 min.

Example 10

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 40, lead - 60. The electrical conductivity of the polymer composition is 8 × 10 ^-3 (Ohm × mm ² / cm) ^-1 , the melt of the polymer composition does not show fluidity.

Example 11

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 80; copper - 20. The resulting polymer composition does not have electrical conductivity, melt flow rate of 14.7 g / 10 min.

Example 12

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 70; copper - 30. The electrical conductivity of the polymer composition is 1 × 10 ^-4 (Ohm × mm ² / cm) ^-1 , the melt flow rate of 9.9 g / 10 min.

Example 13

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 60; copper - 40. The electrical conductivity of the polymer composition is 1 × 10 ^-3 (Ohm × mm ² / cm) ^-1 , the melt flow rate of 2.3 g / 10 min.

Example 14

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 50; copper - 50. The electrical conductivity of the polymer composition is 1.5 × 10 ^-2 (Ohm × mm ² / cm) ^-1 melt flow rate of 0.7 g / 10 min.

Example 15

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 40; copper - 60. The electrical conductivity of the polymer composition is 6.4 × 10 ^-2 (Ohm × mm ² / cm) ^-1 , the melt of the polymer composition does not show fluidity.

Example 16

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 80; aluminum - 20. The resulting polymer composition does not have electrical conductivity, melt flow rate of 16.0 g / 10 min.

Example 17

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 70; aluminum - 30. The electrical conductivity of the polymer composition is 1 × 10 ^-4 (Ohm × mm ² / cm) ^-1 , the melt flow rate is 7.1 g / 10 min.

Example 18

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 60; aluminum - 40. The electrical conductivity of the polymer composition is 1 × 10 ^-3 (Ohm × mm ² / cm) ^-1 , the melt flow rate of 1.5 g / 10 min.

Example 19

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 50; aluminum - 50. The electrical conductivity of the polymer composition is 7 × 10 ^-3 (Ohm × mm ² / cm) ^-1 , the melt flow rate of 0.5 g / 10 min.

Example 20

In the conditions of example 1 at the next load of the components, wt. %: 1,2-SPB - 40; aluminum - 60. The electrical conductivity of the polymer composition is 3.4 × 10 ^-2 (Ohm × mm ² / cm) ^-1 , the melt of the polymer composition does not show fluidity.

Thus, the use of 1,2-SPB as a 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.

Claims (4)

1. An electrically conductive metal-filled polymer composition for 3D printing, consisting of a polymer base, a conductive filler, characterized in that it contains syndiotactic 1,2-polybutadiene (1,2-SPB) as a polymer base, and contains a metal filler as a conductive filler - solder grade POS-63 or lead in the following ratio, wt. %: 1,2-SPB polymer 60-50 Filler 40-50 2. An electrically conductive metal-filled polymer composition for 3D printing, consisting of a polymer base, a conductive filler, characterized in that it contains syndiotactic 1,2-polybutadiene (1,2-SPB) as a polymer base, and contains a metal filler - copper as a conductive filler or aluminum in the following ratio, wt. %: 1,2-SPB polymer 70-50 Filler 30-50