RU2685128C2 - Method of producing high-strength polymer material - Google Patents

Method of producing high-strength polymer material Download PDF

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Publication number
RU2685128C2
RU2685128C2 RU2016151173A RU2016151173A RU2685128C2 RU 2685128 C2 RU2685128 C2 RU 2685128C2 RU 2016151173 A RU2016151173 A RU 2016151173A RU 2016151173 A RU2016151173 A RU 2016151173A RU 2685128 C2 RU2685128 C2 RU 2685128C2
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Russia
Prior art keywords
pressure
constant
component
variable
pressing
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RU2016151173A
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Russian (ru)
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RU2016151173A (en
RU2016151173A3 (en
Inventor
Евгений Константинович Голубев
Александр Никифорович Озерин
Анатолий Михайлович Мартьянов
Тихон Сергеевич Куркин
Олег Владимирович Лебедев
Иван Андреевич Путивский
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Закрытое акционерное общество "Техполимер"
Федеральное государственное бюджетное учреждение науки Институт синтетических полимерных материалов им. Н.С. Ениколопова Российской академии наук (ИСПМ РАН)
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32Component parts, details or accessories; Auxiliary operations
    • B29C43/44Compression means for making articles of indefinite length

Abstract

FIELD: chemistry.
SUBSTANCE: disclosed is a method of producing an oriented film of amorphous-crystalline polymer, which includes a step of pressing the starting polymer in powder form and a step for drawing it, wherein pressure at the pressing step includes a constant component and a variable component. Constant pressure component per one pressing cycle increases from zero to preset value. Variable component for one pressing cycle more than one time can change value from zero to maximum assigned for it. Direction of action of constant and variable pressure components can be directed at angle from 0° up to 90°. Values of amplitude and frequency of variable pressure component can vary according to preset laws.
EFFECT: technical result is improved strength characteristics of article.
9 cl, 5 dwg, 2 ex

Description

The invention relates to the field of obtaining new materials and can find application in the creation of composite materials, characterized by a high set of strength properties. More specifically, the invention relates to a method for producing a material based on a reactor powder of an amorphous-crystalline polymer, for example, ultrahigh-molecular polyethylene (UHMWPE), which has enhanced strength and a number of other properties.

Methods of continuous production of a monolithic billet (sheet, tape, film thread) to obtain a product for subsequent orientational drawing and hardening should combine two processes: transporting the reactor powder to the monolithization device (dosing) and applying pressure with a shift (pressing) to the reactor powder. It is logical that the simplest constructive solution for the pressing unit is rotating rolls (rollers), to which an external compressive load is applied.

In the patent [JP H 07156174], for transporting, direct dosing of the UHMWPE reactor powder onto the moving metal strip is used, which delivers the powder to the pressing zone where pressure is applied from the hydraulic drive.

The efficiency and efficiency of such a device raises certain doubts, primarily due to the complexity of the kinematic scheme used.

However, in subsequent patents, for example, [US 8211342], this scheme is again proposed as the main one, without indicating the detailed construction of the monolithization node, which means, apparently, difficulties in the technical implementation of the node.

The devices based on two rotating rolls [US 8177540 B2, US 8206810 B1] with direct dosing of the reactor powder into the gap between the rolls are promising for further development and relatively simple in terms of technical implementation.

In turn, a device with rollers and direct dosing into the gap [JP H 07156173] can hardly be realized, despite the seeming simplicity of the design, since the processing of three successive pairs of rolls of weakly pressed UHMWPE powder having low mechanical strength on the first and second wolves and filling it in rolls is not possible

Of the other analyzed developments, the technical solution [KR 1002747920000] deserves close attention to use for molding films and film threads from UHMWPE reactor powder rolls of a special configuration (caliber), which makes it possible to confidently work with the amount of pressure applied to the rotating rolls.

As the analysis of the results of the patent research showed, for the orientation drawing of monolithic films of film filaments formed from UHMWPE molded from the reactor powder, standard industrial films are used. equipment used for example in

the production of high-strength polymer (polyethylene,

polypropylene) twine.

The application for the invention from Germany DE No. 102010030706 (published: 01/05/2012) also proposes the use of a planetary design extruder. The method of reactive extrusion for the chemical modification of alkyl polymers or waxes consists in extrusion in an extruder with a planetary device. The independent claim relates to alkyl containing polymers and waxes thus obtained. This design may have advantages in the implementation of the claimed process, however, it seems too difficult to implement.

The technical solution KR 1002747920000 is selected as a prototype.

The objective of the invention is to create a method that allows to obtain composite materials with an extended set of strength and additional characteristics in comparison with known materials at lower loads on equipment.

The technical result of the invention is to expand the range of high-strength polymeric materials, improving the processability of the process, cheapening the production process, increasing its efficiency, increasing equipment life.

Known methods do not allow to obtain the claimed technical result and to solve the problem.

SHORT DESCRIPTION

A method for producing a composite material based on a reactor powder of an amorphous crystalline polymer, such as UHMWPE, is claimed. The polymer in powder form is pressed, preferably between rolls, to produce a long ribbon.

Pressure is applied to the rolls, as a result of which the powder particles, plastically deformed, are joined into a monolithic homogeneous material - a plate or a long (conditionally infinite) ribbon. At the same time, a significant part of the polymer molecules, initially folded into a ball, acquire the same orientation along the preform and partially stretch. As a consequence, increases the strength of the material obtained.

A feature of the proposed method is that the pressing pressure applied to the rolls or to the compression surfaces, in the case of performing compression on other equipment, has two components - a constant and a variable. The direction of action of both components is the same or different at some angle in the range from 0 ° to 90 °. To obtain different properties of the resulting workpiece, the ratio of the efforts of the constant and variable components, the angle between them (0 ° -90 °), and the frequency of application of the variable component vary. At some ratios of efforts, some angles of application of forces and some frequencies of the variable component, a much larger part of the molecules orients themselves along the general direction at lower values of the applied pressures, and in particular at lower values of the constant component of pressure.

The resulting billet is further subjected to deformation, which leads to uniaxial orientation under conditions of orientation drawing under normal conditions or in the presence of excessive external pressure by any known method.

The uniaxial orientation process can be performed at room or elevated temperature.

The uniformity of external pressure in the process of lengthening is possible to achieve in different ways. Preferred is a method of creating external pressure by solid-phase extrusion. For example, one of the possible options, see below.

The process of uniaxial orientation can also be performed by any other known method and in other temperature conditions, which will also mean the use of the proposed method.

The value of the required pressure is selected on the basis of the condition of achieving the yield strength of the material and the formation of intermolecular bonds.

Thus, the claimed technical result has been achieved, namely: obtaining materials with an improved set of strength and additional characteristics and expanding the range of materials obtained, reducing the load on equipment elements, increasing production efficiency.

The achievement of a new technical result was possible due to the fact that due to the use of two compression components - constant and variable - and the correct selection of the frequency of the variable component, it was possible to orient a larger number of polymer molecules in the workpiece and thereby maintain or increase the strength properties of the material while applying lower pressure values, which reduces the requirements for the equipment used and thereby reduces the cost of the production process and improves the quality of the product.

DESCRIPTION OF THE GRAPHIC MATERIAL

FIG. 1 shows a setup diagram for producing a polymeric material in the form of a ribbon from powder of an amorphous-crystalline polymer.

FIG. 2 shows a diagram of pressure applied to compression surfaces (rolls).

FIG. 3 shows a flow chart for the production of a filament from an amorphous-crystalline polymer powder by the subsequent application of pressure, resulting in uniaxial orientation under uniform shear conditions.

FIG. 4a, 4b. The variants of application of constant and variable pressure components are shown.

DETAILED DESCRIPTION.

Accepted notation

1 - amorphous crystalline polymer in powder form.

2 - powder feed hopper.

3 - rolls.

4 - isotropic material (plate, tape).

5 - Pb / Sn alloy lining.

6 - die.

7 - oriented material.

8 - constant pressure component.

9 - variable pressure component.

10 - angle α between the directions of application of the constant and variable components of pressure.

The claimed technical result is achieved by applying the method of obtaining a polymeric material, consisting in the following.

The powder of the amorphous-crystalline polymer is subjected to pressing to obtain plates 4.

At the same time, a portion of the powder is acted upon by a gradually and once increasing pressure, the maximum value of which is taken as the value of the constant component pressure.

In the process of applying a constant pressure component to a portion of the powder in the same direction, an additional pressure is applied, varying in time. Moreover, during the passage of a portion of powdered material through the working zone of the rolls where the constant pressure component reaches its maximum value, the variable pressure changes its value several times. As a result, from the working part of the machine (press, rolls) a plate or a tape of a polymeric material comes out, which is a blank (semi-finished product) for obtaining the final product in the future.

The obtained plate or tape is subjected to uniaxial orientation, by solid-phase extrusion under the influence of external high pressure and uniform shear by any known method.

The inventive method is as follows.

An amorphous-crystalline polymer is used as a starting polymer, for example, UHMWPE in the form of a reactor powder. Particle size can vary widely, preferably from 100 microns to 1500 microns.

The polymer material is obtained in the following way. The amorphous-crystalline polymer in the form of powder 1, loaded into the hopper 2, is pressed into a mold or between the rollers 3 to form plates or a tape 4, respectively. Moreover, the applied pressure contains two components. Conventionally, the constant pressure is 8, which in one pressing operation changes from zero to the maximum value once. And the variable pressure 9, which is applied in the same direction (or at an angle) as the conventionally constant 8, but during one pressing act changes from zero to its assigned value several (assigned number) times.

In the case of rolls 3, the compression force of the rolls is adjusted to the selected maximum value. Then, in the process of pressing, an additional alternating compressive force is applied to the rollers in the direction of compressing the material, the nominal value and frequency of which are designated additionally (separately).

The direction of application of the constant pressure component and the variable component may differ by some angle α 10.

The angle between the direction of action of the constant and variable components of pressure can differ by a value from 0 ° to 90 °.

The ratio of the variable component to the constant may be in the range of 0.01-100, preferably, 0.1-1.5.

The lower limit of the frequency of the variable component can be selected in the range of 0.1 Hz-1000 Hz.

There are several options for the application of additional pressure (Fig. 4). In the process of application, the values of the constant and variable components can be added (Fig. 4a). In addition, the value of the variable component varies in frequency (Fig. 4b) and in amplitude.

The time profile of the variation of the variable component in amplitude and frequency can be set in advance or generated directly during the machine operation, for example, as an adaptation to the response of the material.

In the preferred embodiment, the frequency of the impact of an alternating force is chosen depending on the transport speed during pressing, so that when the compressible material is advanced 100-500 nanometers, the variable component of the compressive force acts 8 or more times. Those. at a transport speed of 0.01 m / s, the frequency of the variable component should be at least 80 kHz - 400 kHz, respectively.

For practical use, the frequency of the variable component ν can be approximately set by the formulas:

ν = (0 ÷ 10 4 ) * ν o

where ν o = ν lin / πD,

ν Lin - linear (transport) speed of movement of the surface of the rolls,

D is the diameter of the rolls.

Theoretical studies and experiments show that when the additional variable component is applied, the required value of the constant component is much lower, and the process productivity is significantly higher.

The effect of constant and variable pressure components can be directed along one axis.

The magnitude of the constant component of the compression force is chosen in the range of 0.01-0.9 of the compression force used in conventional (known) pressing technology, preferably 0.5-0.6.

The force of the variable component of compression can be 0.01-1 of the magnitude of the constant component. It is recommended to choose a value in the range of 0.1-0.3.

Further, these plates or tape are subjected to uniaxial orientation, preferably at room or elevated temperature by, for example, solid-phase extrusion under conditions of uniform shear.

In the preferred embodiment, the solid phase extrusion process under uniform shear conditions is performed by placing the plate between the plates of plastic material 5, for example, Pb-Sn alloy and pushing through the (conical) die plate 6 (FIG. 3). The parameters of the die 6 set the magnitude of the draw ratio. The die size is directly related to the stretch ratio, therefore, to select the preferred size, you must specify the preferred stretch ratio under uniform shear conditions, and this value additionally depends on the size of the polymer molecules and their number in the powdered polymer 1 (matrix). To perform solid-phase extrusion by the proposed method, in a preferred embodiment, Pb-Sn plates of semi-cylindrical shape with a radius of about 5 mm are taken, a blank of 5 × 28 × 0.5 mm is laid over, clamped between semi-cylinders, sent to metal

a plate equipped with a die of the required diameter at the outlet is applied a pressure of at least 200 MPa. Perform a uniform shift, get oriented material 7. In some cases, it is possible to heat the workpiece, but not above the melting point of the material used.

Pb-Sn alloy can be replaced by a suitable plastic substance that can work under the specified conditions and is technologically advanced in use.

Stage pressing can be performed at a temperature of at least 1 ° C below the temperature of the free melting of the polymer, preferably 5 ° C below.

The total draw ratio may be at least 120, preferably 160.

The invention can be illustrated by the following examples.

Example 1. The initial UHMWPE powder is pressed in a special mold under a pressure of 200 atm., At room temperature, to obtain plates with dimensions of 5 × 28 × 0.5 mm. The resulting sample is placed in the plates of plastic alloy Pb / Sn and push it through a conical die plate, providing the multiplicity of drawing material value of 4.5. The sample obtained is characterized by a tensile strength under uniaxial tension of 50 MPa.

Example 2. The original UHMWPE powder is pressed in a special mold under a pressure of 200 atm., At room temperature to obtain plates of size 5 × 28 × 0.5 mm. The resulting sample is placed in the plates of plastic alloy Pb / Sn and push it through a conical die plate, providing the multiplicity of drawing the material value of 4.8. The sample obtained is characterized by a tensile strength under uniaxial tension of 65 MPa.

The inventive method, which allows to obtain materials from an amorphous-crystalline polymer in the form of a powder with an improved complex, mainly strength characteristics, is industrially applicable, since it involves the use of machine tools and equipment commercially produced by industry with minor modifications, and produce products on an industrial scale.

Claims (16)

1. A method of obtaining an oriented material from an amorphous-crystalline polymer in powder form, which includes a stage of pressing the original polymer and a stage of its drawing, and the pressure at the stage of pressing includes a constant component and a variable component,
characterized in that the time profile of the variable component in amplitude and frequency is produced directly during the operation of the machine as an adaptation to the response of the material,
moreover, the constant component of pressure in one pressing cycle increases from zero to the maximum assigned to it,
moreover, the variable component for one pressing cycle more than once changes the value from zero to the maximum assigned to it.
2. A method according to claim 1, wherein the action of the constant and variable components of the pressure is directed along one axis.
3. A method according to claim 1, wherein the angle between the direction of action of the constant and variable components of the pressure differs by from 0 ° to 90 °.
4. A method according to claim 1, wherein the frequency value of the variable component of the pressure varies.
5. The method according to p. 1, in which the ratio of the variable component to the constant is in the range of 0.01-100, preferably, 0.1-1.5.
6. The method according to p. 1, in which the lower limit of the frequency of the variable component is in the range of 0.1 Hz - 1000 Hz.
7. A method according to claim 1, in which the frequency of the variable component ν is given by the formulas:
ν = (0 ÷ 10 4 ) * ν ο
where ν o = ν lin / πD,
ν Lin - linear (transport) speed of movement of the surface of the rolls,
D is the diameter of the rolls.
8. A method according to any one of claims. 1-7, in which the stage of pressing is carried out at a temperature of at least 1 ° C below the temperature of the free melting of the polymer, preferably, 5 ° C below.
9. The method according to any one of paragraphs. 1-7, in which the resulting total degree of extraction is at least 120, preferably 160.
RU2016151173A 2016-12-26 2016-12-26 Method of producing high-strength polymer material RU2685128C2 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100274792B1 (en) * 1998-04-29 2000-12-15 이종학 Continuous production process of high strength and high-modulus polyethylene materials
US20070232469A1 (en) * 2004-03-05 2007-10-04 Bomba Richard D Compliant pressure roller with uniform nip pressure
RU2487798C2 (en) * 2008-06-19 2013-07-20 Тейджин Арамид Б.В. Method of producing polyolefin films

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100274792B1 (en) * 1998-04-29 2000-12-15 이종학 Continuous production process of high strength and high-modulus polyethylene materials
US20070232469A1 (en) * 2004-03-05 2007-10-04 Bomba Richard D Compliant pressure roller with uniform nip pressure
RU2487798C2 (en) * 2008-06-19 2013-07-20 Тейджин Арамид Б.В. Method of producing polyolefin films

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RU2016151173A3 (en) 2018-12-21

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