Extrusion facilitating polyvinylidene fluoride-based agent

FIELD: chemistry.

SUBSTANCE: invention relates to a processing additive for extrusion of polyolefins or thermoplastic resins. The composition contains at least one fluoropolymer (A), at least one inter-phase agent (B) and at least one stabiliser (C). The invention also relates to an extrusion method, which involves: (i) bringing the composition in solid state, as described above in any of claims 1-13, into contact with polyolefin or thermoplastic resin and (ii) extrusion of the mixture obtained at step (i) to obtain a film, pipe, relief or hollow body.

EFFECT: additive reduces or eliminates extrusion defects without reducing the yellowing index of the resin subjected to extrusion.

14 cl, 1 dwg, 1 tbl, 6 ex

 

The technical field to which the invention relates

The present invention relates to technological additive, namely, additive, which makes possible the reduction or elimination of surface defects, which appear in the extrusion of thermoplastic resins, in particular polyolefin. Technological additive (or hereinafter application agent extrusion) contains at least one fluoropolymer (A), at least one interfacial agent (b) and at least one stabilizer (C), possibly diluted with polyolefin (D) with the formation of masterbatches. The invention also relates to the use of an agent extrusion, and extrusion method.

Technical problem

During the extrusion of thermoplastic resins, in particular of polyolefins, especially when receiving sheet can occur heterogeneity of flow at the outlet of the extrusion head, leading to the formation of surface defects and sometimes deterioration of its mechanical and/or optical properties. This phenomenon, in particular, manifests itself in exceeding the critical shear rate. Below this critical speed get smooth extrudates, while above this speed there is the appearance of surface defects. These defects, called “the destruction of the extrusion flow”, exist in several forms. When the speed is x offset, slightly exceeding the critical speed, the film obtained by pneumoperitoneum with extrusion, lose transparency and gloss. At much higher speeds (in other words, at higher performance) observed defects of homogeneity in the form of smooth areas on rough surfaces. These defects significantly degrade the optical and/or mechanical properties of the film. The same phenomenon can be observed in extruded cords. If the surface of the cord loses its gloss and becomes dull and rough, it is often compared with “orange peel”.

Agent extrusion can be added during extrusion of thermoplastic resin, which makes it possible to reduce surface defects. However, it is necessary to add agent extrusion process did not lead to the deterioration index yellowing resin subjected to the extrusion process.

Surprisingly discovered that it is possible the reduction or elimination of defects extrusion without deterioration index yellowing resin subjected to the extrusion process.

Prior art

In patentUSA 6294604 B1the described agent extrusion containing fluoropolymer, polyethylene oxide PEG (PEG), magnesium oxide, and optionally a stabilizer. The stabilizer may be phenolic or fosforsoderzhashchie derivative or a lactone. In the examples described the use of In-225,which is a mixture of Irgafos 168 and Irganox 1010.

PatentsUSA 6214469and6355359described stabilization PE (PE) films with Irganox 1010 (tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenylpropionic)]), PEP-Q (tetrakis-(2,4-di-tert-butylphenyl)-4,4'-biphenylphosphine), or Ultranox 626 (bis(2,4-di-tert-butylphenyl)pentaerythritoltetranitrate), or 627A (Ultranox 626 + MgAlCO3).

In the patent applicationUSA 2003/0225194 A1describes the stabilization of polyolefin mixture of stabilizers consisting of a phenol derivative and two phosphites, one of which can be Ultranox 626 or Ultranox 627.

In the patent applicationUSA 2005/0113494 A1describes the stabilization of polyolefin using a mixture of two phosphites, one of which is considered to have a high activity.

In the patent applicationEP 1616907 A1described Royal blend-based polymer and the interfacial agent, which is used as an agent for extrusion of polyolefins.

In the patent applicationUSA 2005/0010644the described agent extrusion, which is a PEG (PEG), not containing fluoropolymer. Agent extrusion is used for the extrusion of polyolefin, which may contain at least stabilizer. The stabilizer is added to the polyolefin, and not to the agent extrusion process.

In none of these documents is not described composition, such composition according to claim 1.

Drawings

In the drawing 1/1 shows the operation of the pellet press. Product elesmes products to form granulation layer 1, which constantly breaks down the shaft 2, which, in other words, pre-compressed and pressed into the bale channels 3 of the perforated matrix 4. Then a cylindrical pellet 5 out of the matrix 4. The cutter 6, located below the matrix 4, provides the pellets of the desired length.

Brief description of the invention

The invention relates to compositions, including

- at least one fluoropolymer (A),

- at least one interfacial agent (B)

at least one stabilizer (C) of the formula (I)

in which Ar1and Ar2mean aryl group.

Preferably, the stabilizer (C) has the formula (II)

in which R1, R2, R3, R4, R5, R6, R7, R8, R9and R10mean (independently from each other hydrogen atom, a linear or branched alkyl group with1-C20preferably With4-C10or aryl group.

And, more specifically, formula (III)

in which R1, R3, R6and R8each signifies alkyl group with1-C20preferably With4-C10or aryl group.

The composition used as an agent for extrusion of polyolefin or term is plastic resin.

The invention also relates to a method of extrusion, including:

(i) contacting the composition according to one of items 1 to 13 in the solid state with the polyolefin or thermoplastic resin;

(ii) then the extrusion obtained in stage (i) mixture with obtaining films, tubes, relief or hollow body.

Detailed description of the invention

In respect of the fluoropolymer (A)thus marked, any polymer having in its chain at least one monomer chosen from compounds containing a vinyl group capable of polymerization and which contains at least one fluorine atom, an alkyl fluoride group, or forelcosure, directly attached to this vinyl group.

As an example, the monomer can be noted viniferin, vinylidenefluoride (VDF, (WDF), CH2=CF2), triptorelin (VF3), chlorotrifluoroethylene (CTFE (HCFA)), 1,2-defloration, tetrafluoroethylene (TFE (TPV)), HEXAFLUOROPROPYLENE (HFP (HFP)and PERFLUORO(alkylvinyl) ethers.

The polymer may be a homopolymer or a copolymer, and it may also include non-fluorinated monomers, such as ethylene or propylene.

For example, the fluoropolymer is chosen from:

the Homo - and copolymers of vinylidenefluoride (WDF, VDF), preferably containing at least 50 wt.%. WDF (VDF), comonomer choose from chlorotrifluorethylene the (HTFA, CTFE), hexaferrite (HFP, HFP), triptorelin (VF3) and tetrafluoroethylene (TPV, TFE);

the Homo - and copolymers of triptorelin (VF3);

copolymers and, in particular, terpolymers uniting chlorotrifluorethylene (HTFA, CTFE), tetrafluoroethylene (TPV, TFE), HEXAFLUOROPROPYLENE (HFP, HFP) and/or residues of ethylene units and possibly links WDF (VDF) and/or links VF3;

- terpolymers TPV (TFE), HFEs (HFP) and WDF (VDF);

copolymers TPV (TFE), propylene and, optionally, WDF (VDF).

A possible example of a fluoropolymer is terpolymer containing from 30 to 70 wt.% TFE, 10 to 30% HFP and from 5 to 50% VDF or otherwise, containing from 45 to 65 wt.% TFE, from 10 to 20% HFP and from 15 to 35% of VDF, as described in patentUSA 6734252 B1. It can also consist of fluoropolymers described in patentUSA 6380313 B1in particular, terpolymers, including performanceby ether, VDF and HVP. Other examples of fluoropolymers are given in column 6, lines 1-42 patentUSA 6277919 B1.

Mainly, the fluoropolymer is a homopolymer or copolymer of polyvinylidene fluoride (PVDF). He has actually suitable viscosity in the range of vitrification many thermoplastic resins. Preferably, the effectiveness of the agent extrusion is improved if the PVDF contains at least 50 wt.%, more preferably, at least 75% and even more preferably at least 85% VDF. Preferably the, the best effectiveness of the agent extrusion obtained in the case of thermoplastic PVDF. Comonomer is a predominantly HFP. Even more preferably, the copolymer includes only VDF and HPF as monomers.

Preferably, the PVDF has a viscosity of 100 PA·with up to 4000 PA·with a viscosity, measured at 230°C, when the gradient of shear rate 100 s-1using a capillary viscometer. PVDF preferably has a viscosity of 1000 PA·s to 2500 PA·with a viscosity, measured at 230°C, when the gradient of shear rate 100 s-1using a capillary viscometer.

Thus, PVDF called Kynarflex® are perfectly suited for a given composition and a given method.

In respect of the interfacial agent (B)so marked any product that when mixed with component (A) as agent for extrusion improves the efficiency of masterbatches. For example, the interfacial agent (B) can be obtained from:

a) silicones;

b) copolymers of silicone-simple polyester;

c) aliphatic polyesters, such as polybutylene, polylactic acid and polycaprolactones;

d) aromatic polyesters, such as, for example, Diisobutyl ester of phthalic acid;

e) polyethers, such as, for example, polyether polyols and polyoxyalkylene, as, e.g. the, described in the patentUSA 4855360;

f) aminoxide, such as, for example, Occidentalized;

(g) carboxylic acids, such as, for example, hydroxybutanoic acid;

h) esters of fatty acids, such as monolaurate sorbitan.

Without connection with any interpretation, it is possible that the function of the interfacial agent (B) is to stabilize the fluoropolymer (A). He is physically or chemically interacts with the fluoropolymer (A).

Mostly (C) is a simple polyester, preferably selected from oligomers and polymers containing acceleratedly functional group (for example, ethylene oxide or propylene), or polycaprolactone. As an example we can mention polyoxyethyleneglycol, commonly called polyethylene glycol (PEG). Mainly, srednesemennyh molecular weightranges from 400 to 15,000 g/mol (it can be determined, for example, by measuring the viscosity and the melting temperature is in the range from 50 to 80°C. as an example, the PEG can be mentioned Pluriol E® from BASF or Polyglykol® from Clariant. The use of a mixture of two or more polyether not excluded from the scope of the invention.

These PEG and other examples of PEG described in patentsUSA 5587429and5015693. Thus, the said PEG can be obtained from:

- glycol of the formula is N(OS 2H4)nOH, where n is an integer close to 76, from 70 to 80;

- H(OC2H4)d[OCH(CH3)CH2]e(OC2H4)fOH, where d, e and f denote integers and d+f close to 108, from 100 to 110, and e close to 35, 30 to 40;

- Carbowax® 3350 with srednesemennyh molecular weight of about 3500 g/mol;

- Carbowax® 8000 with srednesemennyh molecular weight of about 8000 g/mol;

- Polyglycol® 8000 from Clariant, having srednesemennyh molecular weight of from about 7000 to 9000 g/mol.

Polycaprolacton preferably has srednesemennyh molecular weight of from 1000 to 32000, preferably from 2000 to 10000, and more preferably from 2000 to 4000 g/mol.

In respect of the stabilizer (S)it corresponds to the compound of formula (I):

in which Ar1and Ar2mean aryl group.

Preferably, (C) has the formula (II)

in which R1, R2, R3, R4, R5, R6, R7, R8, R9and R10mean (independently from each other hydrogen atom, a linear or branched alkyl group with1-C20preferably With4-C10or aryl group.

Preferably, (C) has the formula (III)

in which R1, R 3, R6and R8each signifies alkyl group with1-C20preferably With4-C10or aryl group.

As examples of stabilizers can be noted Ultranox 626 GE Specialty Chemicals (bis(2,4-di-tert-butylphenyl)pentaerythritol) CAS No. 26741-53-7, Doverphos S-9228 from Dover Chemical (bis(2,4-dokumenter)pentaerythritol) CAS No. 154862-43-8 and PEP-36 from Amfine Chemical Corporation (bis(2,6-di-tert-butyl, 4-were)pentaerythritol) CAS No. 80693-00-1. Ultranox 626 successfully evaluated, as shown in the following examples.

The stabilizer (S) can be combined with other stabilizers, such as, for example, phenol derivative or a lactone, to enhance its effectiveness. It is also possible to combine several stabilizers (C).

In respect of the polyolefin, which is extruded in the presence of the agent extrusionthe polyolefin can be represented as:

- polyethylene, particularly low density polyethylene (LDPE LDPE), high density polyethylene (HDPE HDPE), medium-density polyethylene, linear low density polyethylene (LLDPE, LLDPE) or ultra-high-density polyethylene (PESIT, UHDPE). It may consist of polyethylene obtained by metallocene catalyst, or, generally, catalyst, called "one" catalyst or Phillips catalyst, or a catalyst of Ziegler-Natta;

- polypropylene, h the particular ISO - or syndiotactic polypropylene;

- biozentrum.uni polypropylene;

- polybutylene (derived from butene-1);

- poly(3-methylbutan) or poly(4-methylpentene).

The case of the extrusion of a mixture of two or more polyolefins, for example a mixture of LLDPE and LDPE, is not a departure from the scope of the invention.

Agent extrusion process is particularly valuable for high-molecular polyethylene and/or polyethylene having a narrow molecular weight distribution (usually such that the index polymolecularity is less than 3, preferably less than 2.5, and even better less than 2.2). It is particularly suitable for the extrusion of polyolefin, particularly polyethylene, upon receipt of a film.

Agent extrusion is also very suitable in the case of polyolefins that contain the absorber acid, such as, for example, hydrotalcite. Found that the presence of hydrotalcite in the polyolefin leads to a significant yellowing in the presence of the agent in the extrusion-based fluoropolymer with interfacial agent, or without it. The stabilizer (S) according to the invention makes it possible to prevent significant yellowing.

Agent extrusion can also be used for the extrusion of other thermoplastic resins, such as, for example, styrene resin, polyester resin or PVC. The styrene resin is geopolitical or a copolymer of styrene containing at least 50 wt.% styrene. It may consist of crystal polystyrene, high impact polystyrene, copolymer of Acrylonitrile-butadiene-styrene (ABS) or alternating copolymer, such as copolymer comprising styrene and a diene. Complex polyester may represent, for example, polyethylene terephthalate (PET, PET) or polybutylene terephthalate (PBT).

The polyolefin or thermoplastic resin may also contain dispersed organic or inorganic particles. The inorganic filler may constitute, for example, silicon oxide, aluminum oxide, zeolite, titanium oxide, carbonate (e.g. sodium carbonate, potassium or calcium), hydrotalcite, talc, zinc oxide, magnesium oxide or calcium, diatomaceous earth, carbon black, etc. It can also consist of inorganic pigment. Organic particles can, for example, to represent the particles of the organic pigment, an antioxidant, or stearate.

In respect of the agent extrusionit includes at least one fluoropolymer (A), at least the interfacial agent (b) and at least one stabilizer (C). (A), (b) and (C)optionally diluted with polyolefin (D) with the formation of masterbatches. Preferably, to maintain its high efficiency, the agent extrusion contains no inorganic filler, in particular of magnesium oxide, and does not contain the polyolefin is.

The corresponding mass fraction (a) and (b) may be such that (a)/(b) is from 10/90 to 90/10, preferably from 30/70 to 70/30, and even better from 30/70 to 60/40. Mass fraction of (C) with respect to (a) and (b) ranges from 0.1 to 20 parts (a) 80-99,9 parts (a) and (B).

If (A), (b) and (C) dilute the polyolefin (D) obtaining masterbatches, mass fraction (A), (b) and (C) ranges from 0.1 to 30%, preferably from 1 to 10%, preferably from 1.5 to 10% and even more preferably from 2 to 10% at 70-99%, respectively, preferably 90-99%, preferably 90-98,5% and even more preferably 90-98% (D).

Agent extrusion is produced by mixing (A), (b) and (C). Then this mixture can be used directly or can be diluted with a polyolefin (D) obtaining masterbatches. Agent extrusion is in the form of powder or granules. Thus, the method of receiving agent extrusion includes:

- phase (i) mixing (A), (b) and (C);

perhaps the stage (ii) diluting the mixture from step (i) of the polyolefin (D).

Phase mixing (i) can be performed using any means for mixing, suitable for thermoplastic materials, such as, for example, an extruder or mixer. You can also mix the three components in the form of powders. Also generally possible using the technology of pressing. It is the introduction of products that are subject to mixing, is in the form of powders pellet mill, and then squeezing the mixture through a die. The figure schematically shows the principle of operation of the press granulator. This device is often used in food industries for production of powder materials of pellet feed for animals. Example press-granulator can be found, for example,EP 0489046.

Press granulator includes a rotating shaft, which provides pressing/mixing powders, and then pressing the mixture formed within the bale channels of the perforated matrix so formed cylindrical pellets, which are then cut using a cutting device positioned below the matrix. Internal friction occurring when mixing the powders in the press, makes it possible to increase the melting temperature of the interfacial agent (B).

Preferably, and to my surprise, achieve high efficiency, if the mixture is produced in such a way that (A) is in solid form, and (B) molten in the mass or on the surface. Preferably, the temperature at which the mixed (a) and (B)are chosen so that the viscosity of (C) was not too low. The temperature is chosen so that:

- interfacial agent (B) was in the molten state in the mass or on the surface and

the fluoropolymer (A) was in the solid state.

Interfacial agent called RA is processed throughout the mass, if it is completely liquid. It is called molten on the surface, if the particles interfacial agent is covered with a molten surface layer and are solid inside. The technology of extrusion is highly suitable for this purpose, but you can also use an extruder operating at reasonably selected and controlled temperature zones.

Stage (i) is preferably carried out at temperatures from 10 to 120°C, mainly from 20 to 100°C, preferably from 40 to 100°C and even more preferably from 60 to 100°C. it Was found that when operating under such conditions, the efficiency is higher than when operating under conditions of a temperature at which (a) and (b) both are in the molten state. At temperatures below 120°C to avoid thermal degradation of the interfacial agent (b)which may affect its effectiveness in the mixture or to lead to yellowing. To ensure thorough mixing preferably, the fluoropolymer (A) was in the form of a powder, in other words, in dispersed form.

Without regard to any particular theory, it is possible that the best effectiveness of the agent extrusion compared with other solutions connected with the fact that (a) and (b) interact physically and/or chemically in the process of stage (i). This method of operation eff is active, than, for example, a process comprising adding masterbatches (a) and masterbatches (B) to thermoplastic resin, for which the contact between (a) and (b) before contacting thermoplastic resin is not desirable. It's also more effective than the method involving the introduction of (a) and (b) separately.

Stage (ii) can be performed using any equipment for mixing polymers known to the person skilled in the art. It can represent, for example, an extruder or mixer. Preferably it represents the extruder.

Mainly for the extrusion of polyolefin choose the polyolefin (D) of the same nature, in other words, it represents, for example, two polyethylene or two polypropylene, preferably having not much different viscosity.

Application

Agent extrusion is used to reduce or eliminate surface defects that appear in the extrusion of thermoplastic resins. It significantly reduces the time to reach a stable defect-free extrusion in the range of parameters of the extrusion, which are typically considered violations caused by extrusion. As it is more effective than the other aforementioned agents extrusion, agent extrusion according to the invention makes it possible to reduce the added amounts of p is relative to the resin, designed for the extrusion, at the same time preventing it from yellowing.

Yellowing as a result of extrusion may be associated with degradation of the extrudable resin and/or polymer and/or interfacial agent. Use one of the stabilizers (C) according to the invention for stabilizing the resin is designed for extrusion, it was known previously, but it does not help to avoid yellowing caused by degradation of the polymer and/or interfacial agent, in certain conditions of extrusion. In fact, even if subjected to extrusion resin stabilized, is not homogeneous inclusion agent extrusion resin in the first zones of mixing extruder, and the stabilizer resin, subjected to extrusion, is not sufficient to stabilize the fluoropolymer and/or interfacial agent.

Agent extrusion process is particularly applicable during extrusion of getting film or extrusion with the receiving tube, relief or hollow body, etc. Besides the already mentioned advantages, helps smooth surface without defects, which is especially important in the case of film, for which you want to obtain good optical properties. Agent extrusion process also makes possible the reduction of pressure in the area of openings of the matrix, and the number of gels. It also allows, to some extent, reduce the raids in the course of a matrix. Agent extrusion used in the form of granules or in powder form.

The contacting agent extrusion and polyolefin or thermoplastic resin is carried out in the solid state prior to extrusion. They can be previously mixed in the solid state or easily introduced into the reservoir of the extruder. Agent extrusion can also be introduced in the molten state to any place inside of the extruder, in which the extrusion of thermoplastic resins, for example, when using a horizontal extruder. The invention also relates to a method of extrusion, which includes:

(i) contacting the agent extrusion in the solid state with the polyolefin or thermoplastic resin;

(ii) then the extrusion of the mixture obtained in stage (i), with film, tube, relief or hollow body.

This method makes it possible to reduce defects during extrusion without harming FE (yellowing index, YI) of polymer that is extruded.

The percentage entered in the polyolefin or thermoplastic resin agent extrusion is preferably such that the number (A)+(B) with respect to the polyolefin or thermoplastic resin is about 30 parts per million (hours/million) up to 100,000 hours/million, mostly from 50 to 5000 hours/million, preferably from 100 to 1000 hours/million

Examples

Products

Use with ewusie products:

HDPE, HDPE:density 0,948 g/cm3the melt viscosity of 0.6 g/10 min (190°C, 2,16 kg) and with the addition of 2000 hours/million Irgafos 168 and 400 hours/million hydrotalcite DHT-4A.

LLDPE, LNPA:Innovex LL0209AA: it consists of a linear low density polyethylene and butene as co monomer density 0,920 g/cm3the melt viscosity of 0.9 g/10 min (190°C, 2,16 kg).

PPA-1, BHK-1: VDF-HFP (11 wt.% HFP) homogeneous PVDF, with a melting point of 140-145°C and a viscosity of 1600 PA·(230°C, 100 C-1).

PPA-2, PARP-2: a mixture obtained by extrusion and comprising, by wt.%:

- 55% of VDF-HFP (10 wt.% HFP) PVDF with a melting point of 166°C and viscosity of 2350 PA·(230°C, 100 C-1);

- 45% PEG with molecular weight close to 8000 g/mol, sold by Clariant under the name of Polyglykol 8000P.

PPA-3, PARP-3: a mixture obtained by extrusion and comprising, by wt.%:

- 49.5% of VDF-HFP (10 wt.% HFP) PVDF with a melting point of 166°C and viscosity of 2350 PA·(230°C, 100 C-1);

- 40,5% PEG with molecular weight close to 8000 g/mol, sold by Clariant under the name of Polyglykol 8000P;

- 10% of an antioxidant sold by GE Specialty Chemicals under the name Ultranox 626.

PPA-4 and PAP-4: Viton Z100, agent extrusion sold by Dupont-Dow.

PPA-5, PAP-5: Viton Z200, agent extrusion sold by Dupont-Dow.

MB-1 (MS-1)- MB-5 (MC-5): each of the PPA (PPA), mentioned above, was included in the fallopian mixture, denoted by MS-i (MB-i) (where i=1-5) and containing 5 wt.% PAP-i (PPA-i) and 95 wt.% LLDPE (LLDPE). D is installed masterbatches received in a twin-screw extruder Haake-2 using the temperature profile 200-220-190-190°C and the speed of rotation of the auger 170 rpm

Examples

Each test was performed in a twin-screw extruder Haake-2 at 220°C with the tank, nitrogen purged.

Example 1 (comparative): (HDPE) was directly subjected to extrusion in the above-mentioned conditions and obtained granules measured with a PI of 7.6.

Example 2 (comparative): a mixture of 98 wt.% HDPE (HDPE) and 2 wt.% MS-1 was obtained by dry blending and then subjected to extrusion in the above-mentioned conditions and obtained granules with the measured FE 14,6.

Example 3 (comparative): a mixture of 98 wt.% HDPE (HDPE) and 2 wt.% MS-2 was obtained by dry blending and then subjected to extrusion in the above-mentioned conditions and obtained granules with the measured FE 10,3.

Example 4 (according to the invention): a mixture of 98 wt.% HDPE (HDPE) and 2 wt.% MS-3 was obtained by dry blending and then subjected to extrusion in the above-mentioned conditions and obtained granules measured with a PI of 8.6.

Example 5 (comparative): a mixture of 98 wt.% HDPE (HDPE) and 2 wt.% The MC-4 was obtained by dry blending and then subjected to extrusion in the above-mentioned conditions and obtained granules with the measured FE 10,8.

Example 6 (comparative): a mixture of 98 wt.% HDPE (HDPE) and 2 wt.% MS-5 was obtained by dry blending and then subjected to extrusion in the above-mentioned conditions and obtained granules measured with a PI of 9.3.

Table I
ExampleMS-iContent PLR (hours/million)FE
1 (comparative)no07,6
2 (comparative)1100014,6
3 (comparative)2100010,3
4 (in accordance with the invention)310008,6
5 (comparative)4100010,8
6 (comparative)510009,3

It was found that for the MC-3, which includes Ultranox 626 may receive a PI of 8.6, while the unstabilized agent extrusion provides IP 14,6.

1. Composition for obtaining agent for extrusion of polyolefin or thermoplastic resin containing
- at least one fluoropolymer(A),
- at least one interfacial agent (B),
at least one stabilizer (C)is selected from bis(2,4-di-tert-butylphenyl)pentaerythritol, bis(2,4-dokumenter)pentaerythritol or bis(2,6-di-tert-butyl, 4-were)pentaerythritol, where
the fluoropolymer (A) is homopolymer or copolymer having in its chain at least one monomer chosen from compounds containing a vinyl group capable of polymerization and which contains at least one fluorine atom, an alkyl fluoride group, or forelcosure, directly attached to this vinyl group;
- interfacial agent (B) selected from
a) silicones;
b) copolymers of silicone-simple polyester;
c) aliphatic polyesters, such as polybutylene, polylactic acid and polycaprolactones;
d) aromatic polyesters, such as, for example, Diisobutyl ester of phthalic acid;
e) polyethers, such as, for example, polyether polyols and polyalkylene;
f) aminoxide, such as, for example, Occidentalized;
(g) carboxylic acids, such as, for example, hydroxybutanoic acid;
h) esters of fatty acids, such as monolaurate sorbitan.

2. The composition according to claim 1, characterized in that the fluoropolymer (A) is chosen from:
the Homo - and copolymers of vinylidenefluoride (VDF), preferably the content is related, at least 50 wt.% VDF, comonomer choose from chlorotrifluorethylene (CTFE), hexaferrite (HFP), triptorelin (VF3) and tetrafluoroethylene (TFE);
the Homo - and copolymers of triptorelin (VF3);
copolymers and, in particular, terpolymers uniting chlorotrifluorethylene (CTFE), tetrafluoroethylene (TFE), HEXAFLUOROPROPYLENE (HFP) and/or residues of ethylene units and possibly parts of VDF and/or VF3;
- terpolymer TFE, HFP and VDF;
copolymers TFE, propylene and possibly VDF.

3. The composition according to claim 1, wherein the interfacial agent (B) is a polyethylene glycol (PEG) or polycaprolactone.

4. The composition according to claim 3, wherein the PEG has srednesemennyh molecular weightfrom 400 to 15,000 g/mol.

5. The composition according to claim 3, characterized in that polycaprolacton has srednesemennyh molecular weight of from 1000 to 32000, preferably from 2000 to 10000, and more preferably from 2000 to 4000 g/mol.

6. The composition according to claim 1, characterized in that the corresponding mass fraction (a) and (b) such that (A)/(b) is from 10/90 to 90/10, preferably from 30/70 to 70/30, and more preferably from 30/70 to 60/40.

7. The composition according to claim 1, characterized in that the mass fraction of (C) with respect to (a) and (b) ranges from 0.1 to 20 parts (a) 80-99,9 parts (a) and (B).

8. The composition according to claim 1, characterized in that (A), (b) and (C) dilute the polyolefin (D), g is e specified polyolefin (D) is selected from polyethylene, in particular low density polyethylene (LDPE LDPE), high density polyethylene (HDPE HDPE), medium-density polyethylene, linear low density polyethylene (LLDPE, LLDPE) or ultra-high-density polyethylene (PESIT, UHDPE); of polypropylene, in particular, ISO - or syndiotactic polypropylene; violentango polypropylene; polybutylene (derived from butene-1); poly(3-methylbutane) or poly(4-methylpentene).

9. The composition according to claim 8, characterized in that the mass fraction of (A), (b) and (C) ranges from 1 to 30%, preferably from 1 to 10%, preferably from 1.5 to 10% and even more preferably from 2 to 10%, respectively 70-99%, preferably 90-99%, preferably 90-98,5% and even more preferably 90-98% (D).

10. The composition according to claim 1, characterized in that the mixture (A), (b) and (C) prepared in the press.

11. The use of a composition according to any one of claims 1 to 10 as a technological additive for polyolefin or thermoplastic resin.

12. The application of claim 11, wherein thermoplastic resin is a styrene resin, polyester resin or PVC.

13. The application of claim 11, wherein the polyolefin contains a neutralizer of acid pollution.

14. The method of extrusion, including:
(i) contacting the composition in the solid state, as defined above in any one of claims 1 to 9, with the polyolefin or thermoplastic the coy resin;
(ii) then the extrusion of the mixture obtained in stage (i), with film, tube, relief or hollow body.



 

Same patents:

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SUBSTANCE: method involves drawing an polyethylene terephthalate article in an adsorption-active liquid medium containing modifying additives, and drying the article in air until complete removal of the solvent. The modifying additive is a biocidal preparation or antipyrene. The polymer article with an extended shape used can be a fibre, a film, a tape, a tube or a rod.

EFFECT: invention simplifies the technology of making polyethylene terephthalate articles with good biocidal properties and low combustibility compared to existing articles.

20 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: copolyether contains an acid component (A) and at least one diol component (B). The acid component consists of 1) 50-60 mol % aromatic polyfunctional acid and 2) 40-50 mol % aliphatic acid, where 90 mol % comprises a natural long-chain dicarboxylic acid selected from azelaic acid, sebacic acid, brassilic acid or mixtures thereof. The invention enables to obtain biodegradable polyether which has over 70% biodegradability after 90 days, density equal to or less than 1.2 g/cm3, average molecular weight 40000-140000, characteristic viscosity 0.8-1.5.

EFFECT: improved characteristics of polyethers.

23 cl, 4 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polyester polymer composition, preparation method thereof, as well as an article moulded from said composition, such as a film, a sheet and a thin-wall hollow container. The polymer composition contains 2-30 wt % polyamide resin (A) 69.5-97.99 wt % polyester resin (B) and 0.01-0.5 wt % polycarboxylic acid (C). The method of preparing the polymer composition involves preparation of a preliminary composition through mixture in molten state of components (A), (B) and (C) or components (A) and (C) with subsequent mixture of the preliminary composition and the polyester resin (B) in molten state. The moulded article is made by moulding the polymer composition.

EFFECT: composition is weakly-coloured and has excellent gas-barrier properties, transparency and mechanical properties of the finished product.

13 cl, 14 tbl, 34 ex

FIELD: chemistry.

SUBSTANCE: invention relates to compositions prepared from polyesters and polyamides for making articles such as sheets, films, fibres, bottles and articles made via pressure casting. The composition contains crystallisable polyester and polyamide dispersed in the polyester. The polyester consists of 85% acid fragments obtained from terephthalic acid, 2,6-naphthalene dicarboxylic acid and diesters thereof. The polyamide consists of a repeating link of aminocaproic acid and a repeating A-D link. A is a residue of adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexane dicarboxylic acid or naphthalene dicarboxylic acid or mixtures thereof, and D is a residue of m-xylene diamine, p-xylene diamine, hexamethylene diamine, ethylene diamine or 1,4-cyclohexane dimethyl amine or mixtures thereof. The polyamide has triamine content after hydrolysis less than 0.22, and content of carboxyl outside the range of 20-80% of total amount of terminal groups.

EFFECT: invention enables to obtain partitioned. granules without increasing relative viscosity and without gel formation.

14 cl, 2 tbl, 4 dwg, 16 ex

FIELD: chemistry.

SUBSTANCE: wall has a layer which contains a polyamide dispersed in a crystallisable polyester and an agent which reduces interphase tension, selected from a group comprising lithium sulphoisophthlate and lithium sulphobenzoic acid. The polyamide contains a product of reacting aminocaproic acid with itself, or a product of reacting A-D, where A is a residue of adipinic, isophthalic, terephthalic, 1,4-cyclohexane dicarboxylic, resorcinol dicarboxylic or naphthalene dicarboxylic acid or mixtures thereof, and D is a residue of m-xylenediamine, n-xylenediamine, hexamethylenediamine, ethylenediamine or 1,4-cyclohexane dimethylamine or mixtures thereof. The polyester contains 85% links obtained from terephthalic acid or dimethyl ester of terephthalic acid. The wall does not contain cobalt compounds.

EFFECT: invention enables to obtain packed articles with high interphase bonding strength and low turbidity.

38 cl, 8 tbl, 5 dwg, 9 ex

FIELD: chemistry.

SUBSTANCE: material contains the following mixture, wt %: polyalkylene terephthalate - up to 100, polycarbonate 1-35, olefin polymer or copolymer - polyethylene, polypropylene, copolymer of ethylene with propylene 1-10, and synthetic wax 0.03-3, selected from a group comprising ester, amide or polyethylene wax. The material also contains 0.1-1 wt % thermal and thermo-oxidative decomposition stabiliser and 0.01-5.0 wt % colouring additive, which is also a polyalkylene terephthalate structuring agent.

EFFECT: invention enables to obtain polyester composite materials with higher melt flow index.

3 cl, 1 tbl, 21 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an oxygen-absorbing composition for making packaging for protecting oxygen-sensitive materials. The composition contains (a) at least one polyester polymer; (b) at least one compound of formula E in amount of approximately 0.1-10 wt % and (c) at least one transition metal in positive oxidation state in amount of 10-400 parts per million. Compound E is a structure of formula (I)

or formula (II)

, where Ar denotes aryl or heteroaryl; R1, R2 and R11 denote H, C1-C12alkyl, C1-C6alkoxy, hydroxy, C2-C6alkenyl; R3, R4, R14 and R15 denote H; R5-R10 and R16 and R17 denote H or C1-C3alkyl; R12 and R13 denote H or C1-C6alkoxy; n and p = 0 or from 1 to 5; q = 0 or from 1 to 4. The invention also relates to walls of packaging containing said composition, a method of making such packaging and a method of packing oxygen-sensitive material in such packaging.

EFFECT: invention enables to obtain articles with high oxygen-absorption and low turbidity.

23 cl, 2 tbl, 19 dwg, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to thermoplastic polymeric compositions for making carpet backing. The composition contains a naturally crystalline or semicrystalline thermoplastic polymer and a nucleating agent - ground glass, glass powder, broken glass or mixtures thereof, in amount of 10-70% in terms of the total weight of the composition and without reinforcing fibre. The composition has properties selected from a group comprising MT4 value less than approximately 0.125 and CT4 value less than approximately 0.1, measured through AACHEN test; time after which surface stickiness disappears less than approximately 1 hour; time for attaining rigidity of the backing less than approximately 75 hours; ignition time greater than approximately 13 seconds and self-extinction time less than approximately 60 seconds.

EFFECT: invention has better processing properties, high fire resistance and enables to make carpet backing with high stability of dimensions and improved crystalline structure.

20 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyester compositions containing oxygen-absorbing polydienes and used in packing food products and drinks. The invention describes a composition which contains a combination or a reaction product (i) resins based on aromatic polyester and (ii) hydrogenated polydiene with terminal hydroxyl groups, where 30-70 mol % monomer links of said polydiene are vinyl links or their hydrogenated residues, and in which 60-80% of initial double bonds remain after hydrogenation. Described also is a method of preparing the composition, involving anionic polymerisation of conjugated diene monomer to form polydiene with terminal hydroxyl groups and mixing the aromatic polyester to obtain polydiene.

EFFECT: good oxygen-absorbing properties and prevention of colouring of polyester compositions during secondary processing.

21 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polymer materials and additives used for heating polymer performs in industrial production of packaging materials for liquids such as bottles for drinks. The invention describes use of inorganic material selected from a group comprising titanium nitride, indium-tin oxide, reduced indium-tin oxide, antimony-tin oxide for improving heating characteristics of the polymer material - polyethylene terephthalate, polypropylene or oriented polypropylene. Described also is a method of improving heating characteristics of the said polymer material, involving bringing the polymer material or one or more monomers for obtaining said polymer through polymerisation into contact with the said inorganic material.

EFFECT: disclosed inorganic material accelerates the heating step when making bottles while lowering amount energy required for heating.

62 cl, 3 dwg, 5 tbl, 24 ex

FIELD: chemistry.

SUBSTANCE: invention can be used in making membrane-electrode blocks used in different types of fuel cells, as well as in portable electronic devices etc. The membranes are obtained through coating from a 5-40% solution prepared from perfluorinated ion-exchange copolymer of tetrafluoroethylene with perfluorosulpho-containing vinyl ester and a tertiary modifying comonomer selected from a group comprising perfluoro-2-methylene-4-methyl-1,3-dioxalane and perfluoroalkylvinyl ester whose alkyl contains 1 or 3 carbon atoms, having equivalent weight of 700-900, number-average molecular weight of 1.0-4.0×105, density 1.79-1.83 kg/m3, degree of crystallinity equal to 1.0-4.5%, and one or more modifying perfluorinated ion-exchange copolymers whose structure is similar to the basic perfluorinated ion-exchange copolymer with equivalent weight of 950-1600, having number-average molecular weight of 4.5-9.0×105, density 1.84-1.91 kg/m3, degree of crystallinity 4.5-12.5%, structural formula: , M denotes H, Li, K, Na, a=23.57-10.53 mol %, b=74.43-81.65 mol %, c=2.0-8.0 mol % in the medium of an organic solvent at 70-120°C. The ratio of the basic perfluorinated and modifying perfluorinated ion-exchange copolymers is equal to 1.5-19. The membrane forms at 40-100°C after evaporation of the solvent.

EFFECT: improved operational properties of the membrane and simple process of making the membrane.

4 cl, 3 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the technology of producing gas-permeable membranes which can be used in fuel cells at high operating temperature (100°C and higher, methanol fuel cells, low- and high-pressure water electrolysis cells etc). The membrane is made from a copolymer of tetrafluoroethylene with perfluorosulpho-containing vinyl ether and a tertiary modifying perfluorinated comonomer - perfluoro-2-methylene-4-methyl-1,3-dioxalane or perfluoroalkylvinyl ether containing 1 or 3 carbon atoms in the alkyl, and a polymeric or inorganic modifier. The method of making the membrane involves contacting a perfluorosulpho-cationite membrane with a liquid composition containing an ion-exchange perfluorosulpho-polymer, a polymeric or inorganic modifier and a solvent. The perfluorosulpho-polymer with functional sulpho-groups SO3M, where M is a hydrogen, ammonium or alkali metal ion, has equivalent mass of 800-900, and is similar on structure to the membrane polymer. Contacting is carried out at 18-80°C. Particles of the modifier are formed on the surface or inside the membrane at 18-120°C.

EFFECT: preserving proton conductivity, preventing cathode polarisation and water flooding, high energy density of fuel cells.

12 cl, 3 tbl, 41 ex

FIELD: chemistry.

SUBSTANCE: perfluoro-elastomer composition contains perfluoro-elastomer, organic peroxide, pre-vulcanisation inhibitor and sodium stearate. Invention enables to obtain a perfluoro-elastomer composition with excellent processability and low-probability pre-vulcanisation. The article moulded from perfluoro-rubber is obtained from thermal cross-linking the perfluoro-elastomer composition.

EFFECT: disclosed article has high ultimate tensile strength and ultimate elongation and low residual compressive deformation.

12 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: water-oil emulsion contains fluoropolymer particles for depositing in liquid form. The emulsion is obtained through homogenisation of the oil component in aqueous phase, preferably already containing fluoropolymer particles and preferably with addition of an emulsifying agent.

EFFECT: emulsion can form dense coatings in a single process, where the said coatings do not crack after drying and roasting.

5 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: material contains an inner layer I, selected from fluoropolymer moulding compound and polyolefin moulding compound. Further, an intermediate layer II is placed, where said layer is made from: a) 2-80 pts. wt polyamine-polyamide graft copolymer; b) 0-85 pts. wt polyether selected from polyethyleneterephthalate, polypropyleneterephthalate, polybutyleneterephthalate, polyethylene-2,6-naphthalate, polypropylene-2,6-naphthalate and polybutylene-2,6-naphthalate; c) 0-85 pts. wt polymers selected from polyamides, fluoropolymers and polyolefins and d) at most 50 pts. wt additive selected from shock resistant rubber and/or conventional auxiliary substances and fillers. Component a) is obtained using the following monomers: 0.5-25 wt % polyamine graft copolymer containing at least four nitrogen atoms, as well as polyamide-forming monomers selected from lactams, ω-aminocarboxylic acids and/or equimolar combinations of diamine and dicarboxylic acid. The sum of weight parts of a), b) and c) equals 100. Layer III made form polyether moulding compound then follows.

EFFECT: obtained material has higher bonding strength of layers.

15 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: aqueous dispersion contains A) 0.05-10 wt % salts of perfluoropolyester derivatives of dicarboxylic acids of formula T-O-Rt-T, where T = -CF2-COOZ or -CF2CF2-COOZ, Z - Na, K, NH4, R1(R2)(R3)N, R1=R2=alkyl or hydroxyalkyl, R3 = H, alkyl or hydroxyalkyl, Rf denotes (per)fluoropolyoxyalkylene chain with number-average molecular weight of 500-10000, and B) 0.01-5 wt % water-dispersible or water-soluble cationogenic polymers with charge density in dry polymer greater than 1 mEq/g. The dispersion is obtained by dispersing 0.05-10 wt % component (A) in water. Cationogenic polymer (B) is slowly added to the obtained dispersion while stirring until achieving weight ratio of (A) to (B) of 1:1-5:1.

EFFECT: dispersions which endow paper with improved oil-repellent properties against compounds with high content of fat or fatty acids.

14 cl, 16 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the technology of making cold shrink articles which are used in splicing and protecting sections of wires or cables, different seals and/or insulation of substrates from adverse effects of the external medium in automobile, aerospace, power generation, telecommunication, chemical and defense industry. The cold shrink composition for moulding a tubular elastomeric article having residual deformation less than approximately 35% contains a fluoroelastomer; a homopolymer of epichlorohydrin or polymers obtained from epichlorohydrin; and a peroxide cross linking agent. A cold shrink article is made from the said composition, having an elastomeric element in stretched state and a core which holds the elastomeric element in stretched state and made with possibility of removal. The method of making the cold shrink article involves mixing said components; moulding the obtained composition into an elastomeric article; stretching at least part of the elastomeric article; and inserting the core which is made with possibility of subsequent removal into the stretched part of the elastomeric article.

EFFECT: obtaining articles which are resistant to tearing at high temperatures.

10 cl, 8 dwg, 5 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention discloses fluorinated elastomer latex which contains an aqueous medium, a fluorinated elastomer dispersed in the aqueous medium in amount of 10-60 wt %, and a fluorinated emulsifying agent of formula (1): C2F5OCF2CF2OCF2COOA, where A is a hydrogen atom, an alkali metal or NH4 which has excellent dispersion stability. Disclosed is a fluorinated elastomer obtained through coagulation of fluorinated elastomer latex, which has low content of emulsifying agent, as well as a product moulded from fluororubber obtained by cross-linking the fluorinated elastomer and which has excellent physical properties.

EFFECT: improved environmental and sanitary-technical properties of the elastomer and improved properties of the fluororubber.

8 cl, 2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: described is a polymer composition formed from molten mass, containing: (a) non-fluorinated polymer formed from molten mass; and (b) fluoropolymer obtained from copolymerisation (1) from 20% to 30% of total weight of vinylidene fluoride; (2) one or more fluorinated monomers which are not vinylidene fluoride, and (3) one or more modifiers which are selected from (i) olefins containing a bromine or iodine atom bonded to the carbon atom of the olefin double bond, (ii) olefins of formula (IV): Xa2C = CXa-Rf-(Xb)r (IV), where each Xa can independently represent hydrogen, fluorine, chlorine, Rf represents a perfluoroalkylene group, perfluorooxyalkylene group or perfluoropolyester group; Xb represents Br or I or r equals 1, 2 or 3, and (iii) a mixture of these substances; also content of one or more modifiers is not more than 1 wt %, is sufficient for formation of a long, branched chain of a fluoropolymer without formation of gel, where the composition contains 0.005-50 wt % fluoropolymer, the non-fluorinated polymer being that, which does not contain fluorine atoms or contains fluorine atoms with ratio of fluorine atoms to carbon atoms less than 1:1, the fluoropolymer has a fluorinated chain in which the ratio of fluorine atoms to carbon atoms is at least equal to 1:1. Also described is a polymer fusible additive composition for use as an additive during extrusion of non-fluorinated polymer.

EFFECT: increased effectiveness of the composition.

10 cl, 12 ex, 8 tbl

FIELD: chemistry.

SUBSTANCE: described is a fluoropolymer latex which contains a fluoropolymer and fluorine-containing emulsifier of formula (1): F(CF2)4OCF2CF2OCF2COOA, where A is a hydrogen atom, alkali metal or NH4. A method is also described for producing such latex, and a fluoropolymer, which is obtained by coagulating fluoropolymer latex. The fluoropolymer latex can be used as an agent for coating different materials, such as metallic substrates, inorganic oxide substrates, polymer substrates, synthetic fibre, glass fibre, carbon fibre or natural fibre.

EFFECT: fluoropolymer is useful as material with excellent heat resistance, oil resistance, chemical resistance, weather resistance, non-stickiness, anti-overgrowth properties, water-repellent properties, oil-repellent properties, solvent-repellent properties.

7 cl, 2 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: wood-polymer composition for articles contains polyvinyl chloride, wood flour, calcium-zinc complex stabiliser and the composition can additionally contain a metal-containing lubricant obtained via reaction of higher monocarboxylic acids with glycerine at 130-230°C in molar ratio 1:(1-2) in the presence of oxides of divalent metals Ca, Zn, Mg or other two-component mixtures in weight ratio 0.25-1.0:0.5-1.0 and polyethylene wax.

EFFECT: high quality of ready articles owing to improved technological parameters of the compositions, thermal stability, melt fluidity, water absorption and environmental safety.

2 cl, 1 tbl

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