EP3237171A1

EP3237171A1 - Extrusion agent for polyolefins extrudable in the form of fibres

Info

Publication number: EP3237171A1
Application number: EP15817984.6A
Authority: EP
Inventors: Samuel Devisme; Jérôme CHAUVEAU; François Beaume; James T. Goldbach; David A. SEILER
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2014-12-22
Filing date: 2015-12-10
Publication date: 2017-11-01
Also published as: FR3030528A1; WO2016102796A1; FR3030528B1; US20170368731A1

Abstract

The invention relates to an extrusion-assisting agent containing low-viscosity thermoplastic fluorinated polymers and preferably not containing a synergist. The invention also relates to the use of the extrusion agent for extrusion in the form of monofilament or multifilament fibres or non-woven materials, and to the extrusion method.

Description

EXTRUSION AGENT FOR EXTRUDABLE POLYOLEFINS AS FIBERS

FIELD OF THE INVENTION

The present invention relates generally to the field of extrusion of thermoplastic polymers. More particularly, the invention relates to an extrusion assisting agent, that is, an additive which makes it possible to reduce or eliminate the surface defects that occur when extruding a thermoplastic resin, in particular a polyolefin, in the form of fibers. The extrusion aid according to the invention (or extrusion agent in the following application) contains thermoplastic fluoropolymers of low viscosity and does not contain a synergist. The invention also relates to the use of the extrusion agent for extrusion in the form of single or multi-filament fibers or nonwovens, as well as to the extrusion process.

TECHNICAL BACKGROUND

During the extrusion of the polyolefms, irregularities in the flow and / or deposits may appear at the outlet of the die, which results in surface defects and sometimes the deterioration of the mechanical properties of the extruded polyolefin. The addition of an extrusion agent in the polyolefin to be extruded makes it possible to reduce these defects or even to eliminate them.

US 4013622 discloses the use of polyoxyethylene glycol (PEG) as an extrusion agent.

It is known to use fluoropolymers as extrusion agents, as described in US 3125547 and US 4581406, which discloses the use of fluoroelastomers.

Numerous documents describe the use of extrusion agents comprising fluorinated polymers mixed with synergists, and possibly other additives. The Applicant has already described in EP 1616907 the use of a mixture of at least one fluorinated polymer and at least one interface agent, as an extrusion agent for the extrusion of a polyolefin in the form of of movie.

US 4855360 and US 5587429 disclose the use of a fluoroelastomer in combination with a polyoxyalkylene to improve the conversion of hydrocarbon polymers. However, it has been found that the use of fluoroelastomers as an extrusion agent fails to eliminate the extrusion defects of all types of polyolefins, especially those of low viscosity, having a melt flow index. at least 10 g / 10 min, preferably greater than 25 g / 10 min. Indeed, in this case the use of fluoroelastomers as extrusion agent does not give satisfactory results to eliminate or at least reduce the surface defects, because these compounds do not disperse homogeneously in the mass of said polyolefin.

There is therefore a need to prepare new extrusion agents based on fluoropolymers, which improve the extrusion of polyolefins of low viscosity, especially in the form of fibers.

SUMMARY OF THE INVENTION

The invention relates firstly to an extrusion agent for polyolefin extrudable in the form of fibers, said extrusion agent comprising a vinylidene fluoride-based polymer (hereinafter referred to as "PVDF") having a thermoplastic character.

Typically, said PVDF has a viscosity of less than 5 kP, preferably less than 1 kP, as measured at 232 ° C and 100s- ¹ by means of a capillary rheometer or a parallel plate rheometer. the invention has a molecular weight ranging from 5,000 to 200,000 Dalton, as measured by size exclusion chromatography.

Advantageously, the extrusion agent according to the invention is free of synergist. By the term "synergist" is meant here an interface agent (surfactant) which is a thermoplastic oligomer or polymer in the liquid state or is melted at the extrusion temperature and has a lower melt viscosity. to that of the polymer to be extruded and additives used. Many synergists are used in combination with a fluoropolymer to enhance the positive effects of the latter during the extrusion of polyolefins.

It has now been found that the extrusion agent according to the invention makes it possible to obtain good results during the extrusion of polyolefins, such as a drop in pressure, an improved surface state and a lack of deposits. The extrusion agent according to the invention is particularly effective in reducing or even eliminating extrusion defects likely to occur during the extrusion of low viscosity polyolefins having a high melt index of at least 10 g / 10 min, preferably greater than 25 g / 10 min, advantageously greater than 40 g / 10 min, measured according to ASTM 1238.

According to a second aspect, the invention relates to fibers extruded from a formulation comprising a polyolefin and the extrusion agent of the invention. These fibers are in the form of mono- or multi-filaments, or in the form of non-woven materials. One of the advantages provided by the extrusion agent according to the invention is that it makes it possible to obtain good quality fibers from low viscosity polyolefms, for which the use of a fluoroelastomer as an agent extrusion (alone or in admixture with a synergist), does not give satisfactory results, because of its high viscosity and elasticity, which prevent the homogeneous dispersion in the mass of the polyolefin.

According to another aspect, the invention relates to a process for producing fibers by extrusion of a polyolefin by means of the extrusion agent of the invention, said polyolefin having a melt index of at least 10 g. / 10 min, preferably greater than 25 g / 10 min, advantageously greater than 40 g / 10 min, said process comprising the following steps:

at. adding said extrusion agent to the polyolefin formulation, and b. extrusion of the final polyolefin formulation into fibers. DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The invention is now described in more detail and without limitation in the description which follows.

According to a first aspect, the invention relates to an extrusion agent for extruded polyolefin in the form of fibers, said extrusion agent comprising a vinylidene fluoride-based polymer (PVDF) having a viscosity of less than 5 kP, preferably less than at 1 kP, and having a thermoplastic character.

According to one embodiment, said polymer is a PVDF homopolymer.

According to another embodiment, the PVDF is a copolymer of fluoride of VDF and at least one other comonomer chosen from chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoroethylene (VF3), tetrafluoroethylene (TFE) and ethylene. Advantageously, said copolymer contains at least 75% by weight of VDF, preferably at least 85% by weight of VDF, which gives it a thermoplastic character. These polymers can be obtained by known polymerization methods such as solution, emulsion or suspension polymerization. According to one embodiment, the PVDF is prepared by an emulsion process in the absence of fluorinated surfactant.

The PVDFs according to the invention are characterized by a low melt viscosity, namely a viscosity ranging from 0.01 to less than 5 kP, preferably from 0.03 to 2.5 kP, advantageously of 0.05. at less than 1 kP, and more preferably from 0.1 to 0.8 kP. The viscosity is measured at 232 ° C., at a shear rate of 100 sec ^-1 using a rheometer of a capillary rheometer or a parallel plate rheometer, according to ASTM D3825. give similar results.

These PVDFs have number average molecular weights ranging from 5 kDa to 200 kDa, preferably from 10 kDa to 100 kDa, as measured by 0.003M DMF / LiBr steric exclusion chromatography with PMMA as a calibration standard. These low molecular weight PVDFs can be obtained using high levels of one or more chain transfer agents. According to one embodiment, chain transfer agents adapted to this purpose are chosen from:

short chain hydrocarbons, such as ethane and propane,

esters, such as ethyl acetate and diethyl maleate,

alcohols, carbonates, ketones,

halocarbons and hydrohalocarbons, such as chlorocarnides, hydrochlorocarbons, chlorofluorocarbons and hydrochlorofluorocarbons, organic solvents, when added to an emulsion or suspension polymerization reaction.

Other factors favoring the production of low molecular weight polymers are the conduct of the polymerization reaction at high temperatures, or the use of high levels of initiator.

The PVDFs forming part of the extrusion agent according to the invention are preferably homogeneous copolymers, this term meaning that they have uniform chain structures in which the statistical distribution of the comonomer (s) along the chain polymer is tightened.

This particular distribution of comonomer distinguishes these polymers (called "homogeneous") from those called "heterogeneous" which are characterized by the fact that the polymer chains have a distribution in average comonomer content which is multimodal or spread; the heterogeneous PVDF therefore comprises polymer chains rich in comonomer and chains comprising almost no or little comonomer. The Applicant has described heterogeneous PVDFs and extrusion agents containing them in EP 1976927.

The homogeneous PVDF copolymers are prepared by a one-step process, in which the VDF and the comonomer are gradually injected, maintaining a constant VDF / mono monomer mass ratio.

One or more additives may be added to the PVDF described above to form the extrusion agent according to the invention. These additives are advantageously chosen from the primary antioxidants of phenolic or phenolic hindered type, and / or secondary selected from phosphorus components (phosphonites and / or phosphites). Amines can also be used, but in general their use must be limited because of possible interactions with PVDF.

According to a second aspect, the invention relates to fibers extruded from a formulation comprising a polyolefin and the extrusion agent of the invention. These fibers are in the form of monofilaments or multi-filaments, or in the form of nonwoven materials which are groups of randomly oriented or directional fibers in the form of a web, a web or a web. fiber mattress. The diameters of these fibers range from 0.1 to 300 microns, advantageously from 0.5 to 5 microns (for nonwovens), from 5 to 50 microns (for multi-filaments), from 50 to 300 microns (for monofilaments). These diameters are given for information only. These fibers are used in many fields such as textiles (clothing, architecture, industrial) and filtration (air, liquids such as water or fuels).

According to another aspect, the invention relates to a process for producing fibers by extrusion of a polyolefin by means of the extrusion agent of the invention, said polyolefin having a melt index of at least 10 g. / 10 min, preferably greater than

25 g / 10 min, advantageously greater than 40 g / 10 min, said process comprising the following steps:

at. adding said extrusion agent to the polyolefin formulation, and b. extrusion of the final polyolefin formulation into fibers.

The extrusion agent can be added to the final formulation in a pre-compounding or dry-mix phase during extrusion via the use of a masterbatch. In the latter case, the extrusion agent is diluted in a polyolefin formulation having the same viscosity as the polyolefin formulation to be extruded. The extrudable thermoplastic resin in the form of fibers may be a polyolefin, a styrenic resin, a polyester or a polyamide / copolyamide.

The polyolefin is chosen from:

• a polyethylene, in particular a low density polyethylene (LDPE), high density (HDPE), linear low density (LLDPE), very high density (UHDPE).

polypropylene, in particular iso- or syndiotactic polypropylene;

It would not be departing from the scope of the invention in the case of the extrusion of a mixture charged with two or more polyolefms.

The term "styrenic resin" denotes a homopolystyrene or a copolymer of styrene containing at least 50% by weight of styrene. It may be a crystal polystyrene, a high impact polystyrene, an acrylonitrile-butadiene-styrene copolymer (ABS) or a block copolymer, for example a copolymer comprising styrene and a diene.

The polyester may be for example poly (ethylene terephthalate) (PET) or poly (butylene terephthalate) (PBT).

The polyamide and copolyamide may be, for example, PA6, PA6.6, PA6.6 / 6,

PA6.10, PA12, PA10.10, PAU, this list not being restrictive.

The thermoplastic resin may be charged, that is to say contain dispersed organic or inorganic particles. The inorganic filler may be for example a silica, an alumina, a zeolite, a titanium oxide, sodium or potassium carbonate, hydrotalcite, talc, a zinc oxide, a magnesium or calcium oxide, a diatomaceous earth or carbon black. It can also be a mineral pigment. The organic particles may be for example those of an organic pigment or an antioxidant. The organic filler may be antioxidants, but also UV absorbers, HALS, slipping agent, anti-blocking agent, anti-fogging agent or anti-water repellent.

In a particular case, the polyolefin is a polypropylene having a melt index of at least 10 g / 10 min, preferably greater than 25 g / 10 min, advantageously greater than 40 g / 10 min, measured according to ASTM standard 1238 .

EXAMPLES

The following examples illustrate the invention without limiting it.

Example 1

A high pressure autoclave having an inner volume of 2 1 is charged with 1000 ml of deionized water and 0.6 g of Pluronic ^® 31R1 surfactant. The autoclave is purged with nitrogen with rapid stirring for 20 min. The vent valve is closed, 5.0 g of propane is added and the mixture is heated to 83 ° C. 140 g of vinylidene fluoride (VDF) are then added to reach a pressure of 44.8 bar. While continuing to stir the contents of the autoclave, 1% by weight of a potassium persulfate solution and 1% by weight of a sodium acetate solution (total solids content of 2% by weight) are added. weight) at a flow rate of 3.0 ml / min until the pressure begins to drop, then the flow rate is decreased to 0.5 ml / min. The addition of VDF continues to maintain the pressure at 44.8 bar. When the amount of VDF added is 400 g, the supply of VDF and initiator is stopped and the reaction is maintained at 83 ° C until the pressure drops below 20.68 bar; at this point the autoclave is vented and cooled to room temperature. 1.3 liters of a fluid white latex are obtained. The latex is dried at 110 ° C. for 12 hours in an oven to obtain dry fragments. The latex has the following characteristics:

particle size: 276 nm;

solids content: 30.2% by weight;

melt index: 0.4 kP (232 ° C, 100s ¹ );

weight average molecular weight: 105.7 kDa, as measured by 0.02M DMF / LiBr size exclusion chromatography with PMMA as standard of calibration, number average molecular weight: 52.7 kDa;

melting temperature: 170.7 ° C, measured by differential scanning calorimetry (DSC) second heating cycle.

Examples 2-6: PVDF Homopolymers

A high pressure autoclave with an internal volume of 352.4 l is charged with 149.3 l deionized water and 720 g Capstone ^® FS-10 fluorinated surfactant (30 wt% solution). The autoclave is purged with nitrogen; the aeration valve is closed, ethyl acetate (CTA) is added and the mixture is heated to 83 ° C. Vinylidene fluoride (VDF) is then added to reach a pressure of 44.8 bar. While continuing to stir the contents of the autoclave, 3.629 kg of a first solution of potassium persulfate at 1.65% by weight and a second solution of sodium acetate at 1.65% are added rapidly. by weight (total solids content: 3.3%). Following a short induction phase, the initiator solution is added continuously at a rate of 0.227 to 1.361 kg / h. The addition of VDF continues to maintain the pressure at 44.8 bar. When the amount of VDF added is 96.162 kg, the supply of VDF and initiator is stopped and the reaction is maintained at 83 ° C until the pressure drops below 20.68 bar; at this point the autoclave is vented and cooled to room temperature. About 272,156 kg of fluid white latex are obtained. The latex is diluted to 20% by weight and spray-dried. The latex has the following characteristics shown in Table 1:

particle size: about 300 nm;

mass ratio of solids: 30%;

melt index: measured at 232 ° C, 100s- ¹ using a capillary rheometer or a parallel plate rheometer;

melting temperature: measured by differential scanning calorimetry (DSC) second heating cycle.

Examples 7 and 8: VDF / HFP Copolymers

A high-pressure autoclave having an inner volume of 352.4 1 was charged with 156.49 1 of deionized water and 66 g of Pluronic ^® 31R1 surfactant. The autoclave is purged with nitrogen; the aeration valve is closed, ethyl acetate is added and the mixture is heated to 83 ° C. While continuing to stir the contents of the autoclave, 8.3 kg of hexafluoropropylene (HFP) are quickly added and VDF is then added to reach a pressure of 44.8 bar. While continuing to stir the contents of the autoclave, 2.95 kg of a first solution of potassium persulfate at 1% by weight and a second solution of sodium acetate at 1% by weight are added rapidly. (total solids content: 2%). Following a short induction phase, the initiator solution is added continuously at a rate of 0.227 to 1.361 kg / h. The addition of HFP and VDF continues to maintain the pressure at 44.8 bar. When the amount of VDF added reaches 7.484 kg and the amount of HFP at 2.042 kg (9.526 kg in all), the supply of VDF, HFP and initiator is stopped and the reaction is maintained at 83 ° C. until that the pressure drops below 20.68 bar; at this point the autoclave is vented and cooled to room temperature. About 24.95 kg of fluid white latex are obtained (its solids content being 33%). The latex is diluted to 20% by weight and spray-dried to obtain a white powder.

Its characteristics are presented in Table 1 ("n / d" means "not determined".

The HFP mass content of the copolymer was determined by magnetic resonance spectroscopy ( ¹⁹ F NMR). Rheology molten state% by weight

CTA load Flow index

(kP, @ 100s ^" \ Tf of HFP in the

Ex. G CTA / kg VDF or kP, @ 100s ^"

230 ° C, plates e / Kg (VDF + HFP) 230 ° C, capillary (° C) Copolymer parallel)

2 23.6 1, 2 1, 2 170.6 -

3 28.3 0.7 0.62 171, 4 -

4 35.4 0.4 0.25 171, 4 -

5 47.2 0, 1 0, 1 1 171, 8 -

6 76.0 <0.1, 0.04 172.4 -

7 12.4 4.0 n / a 123.9 17.4

8 15.7 1, 7 n / a 123.9 17.6

Table 1

Example 9

Granules of a PVDF homopolymer medium viscosity: 3-4 kP are incorporated by twin screw extrusion at 5% by weight in a type of polypropylene Sabic PP ^® 511 A, MFI 25 g / 10 min at 230 ° C, 2.16 kg. This masterbatch, which is in the form of granules, is then tested as an aid for implementation according to the protocol described below:

extrusion at 230 ° C. on an extruder from the company Collin with a screw diameter of 30 mm, L / D = 25 with a capillary die 0.5 mm in diameter and 10 mm in length;

after 15 minutes of extrusion said master batch is introduced at 1% by weight.

90 minutes after the introduction of the masterbatch, a pressure drop of about 10 bar and an improved surface appearance are observed.

Example 10

Homogeneous VDF / HFP copolymer granules (mass content of HFP: 18-20%, average viscosity: 0.4-0.5 kP) are incorporated by twin-screw extrusion at a level of 5% by mass in a Sabic-type polypropylene. ^® PP 511A, MFI 25 g / 10 min at 230 ° C, 2.16 kg. This masterbatch, which is in the form of granules, is then tested as an aid for implementation according to the protocol described below: extrusion at 230 ° C. on an extruder from the company Collin with a screw diameter of 30 mm, L / D = 25 with a capillary die 0.5 mm in diameter and 10 mm in length;

after 15 minutes of extrusion said master batch is introduced at 1% by weight.

90 minutes after the introduction of the masterbatch, a pressure drop of about 20 bar and an improved surface appearance are observed.

Example 11

PVDF pellets from the synthesis example 5 (viscosity about 0.11 kP) are incorporated by twin screw extrusion at 5% by weight in a polypropylene type Sabic ^® 511A PP, MFI 25 g / 10 min at 230 ° C, 2.16 kg. This masterbatch, which is in the form of granules, is then tested as an aid for implementation according to the protocol described below:

extrusion at 230 ° C. on an extruder of the company Collin with a screw diameter of 30 mm, L / D = 25 with a capillary die of 0.5 mm diameter and a length of 10 mm;

after 15 minutes of extrusion said master batch is introduced at 1% by weight.

90 minutes after the introduction of the masterbatch, a pressure drop of about 15 bar and an improved surface appearance are observed.

Claims

Extrusion agent for polyolefin extrudable in the form of fibers, said extrusion agent comprising a vinylidene fluoride-based polymer (PVDF) having a viscosity of less than 5 kP, a molecular weight ranging from 5 to 200 kDa measured by chromatography of Steric exclusion, and having a thermoplastic character, the viscosity being measured at 232 ° C, at a shear rate of 100 s ^"1 according to ASTM D3825.

An extrusion agent according to claim 1 wherein said PVDF is a PVDF homopolymer.

An extrusion agent according to claim 1 wherein said PVDF is a copolymer comprising vinylidene fluoride (VDF) and at least one other comonomer selected from chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoroethylene (VF3) ), tetrafluoroethylene (TFE) and ethylene, said copolymer containing at least 75% by weight of VDF.

An extrusion agent according to one of the preceding claims wherein said PVDF has a viscosity of less than 1 kP.

An extrusion agent according to any one of the preceding claims wherein said PVDF has a molecular weight of from 10 to 100 kDa measured by size exclusion chromatography.

Extrusion agent according to one of claims 3 to 5 wherein said PVDF is a homogeneous copolymer.

7. extrusion agent according to one of the preceding claims for the extrusion of a polyolefin with a melt index of at least 10 g / 10 min, preferably greater than 25 g / 10 min, advantageously greater than 40 g / 10 min when measured at 230 ° C and 2.16 kg (ASTM Standard 1238).

8. extrusion agent according to claim 7 characterized in that said polyolefin is a polypropylene.

9. extrusion agent according to one of the preceding claims characterized in that it is free of synergist.

10. extrusion agent according to one of the preceding claims comprising an additive selected from antioxidants.

11. Fibers extruded from a formulation comprising a polyolefin and an extrusion agent according to any one of claims 1 to 10.

12. Fibers according to claim 11 characterized in that said polyolefin has a melt index of at least 10 g / 10 min, preferably greater than 25 g / 10 min, preferably greater than 40 g / 10 min.

13. Fibers according to one of claims 11 and 12, said fibers being mono or multi-filaments.

14. Fibers according to one of claims 11 and 12, said fibers being in the form of groups of oriented fibers, to form non-woven materials.

15. Process for extruding a polyolefin in the form of fibers by means of an extrusion agent according to any one of claims 1 to 10, said polyolefin having a melt index of at least 10 g / 10 min, preferably greater than 25 g / 10 min, advantageously greater than 40 g / 10 min, said process comprising the following steps:

The process according to claim 15, wherein in step a) comprises compounding said extruder into the polyolefin formulation.

The method of claim 15, wherein in step a) said extrusion agent is first diluted in a polyolefin formulation having the same viscosity as the polyolefin formulation to be extruded, to form a masterbatch which is added, in a second step, to said polyolefin formulation.