JPH05247287A - Additive composition to increase stability of polymer - Google Patents

Abstract

PURPOSE: To provide an additive composition to increase processing stability of a polymer.

CONSTITUTION: The additive composition to increase processing stability of polymer of 4-methyl-1-pentene, comprising a mixture of at least one hindered amine and at least one phosphite compound, the ratio of the hindered amine to the phosphite compound being in the range of (about 0.1 - about 10): (about 0.1 - about 10), the hindered amine being, for example, a dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-pyperidine ethanol and the phosphite compound being, for example, bis (2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite triisopropyl amine.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

This invention relates to the process stability and optionally UV stability of polymers of 4-methyl-1-pentene,
The present invention relates to an additive composition for improving other properties such as heat stability and pinch sealability.

[0002]

Polyolefins are processed into various end products for use. This processing can be performed by blow molding, injection molding or extrusion molding. Regardless of the processing technique used, the polyolefin is subjected to processing stress during this period. Due to this processing stress, also known as shear stress, long polyolefin chains split apart. The air oxidation and high temperatures required to process polyolefins are probably the major contributors to this phenomenon. The severity of decomposition a polyolefin undergoes can be measured by monitoring its melt flow rate. There is also a correlation between the molecular weight, viscosity, and melt flow rate of a particular polyolefin. The lower the molecular weight, the lower the viscosity and the higher the melt flow rate.

[0003]

Due to these processing stresses, decomposition occurs and as a result the melt flow rate of the polyolefin changes. These changes, in turn, complicate the processing operation to the extent that constant constant adjustments in extrusion speed and other processing conditions are required. At a minimum, this set of results makes inefficient use of time, materials and labor.

It is therefore most desirable to keep it constant, especially during processing, or to allow only minimal changes in the flowability of the polyolefin. One way to achieve this goal is to improve the polyolefin's ability to resist processing stress. Therefore, providing an additive package that can increase processing stability is an important contribution to the industry.

Polyolefins undergo decomposition when exposed to light, heat, oxygen and gamma rays, which results in the deterioration of their physical properties. Hindered amines, without limitation
Various agents including hindered phenols, benzophenones, benzotriazoles, phosphites and / or diphosphites have been used extensively or in combination to minimize the degradation of polyolefins. Traditionally, hindered amines are used with phosphites or diphosphites.

Hindered amines are commonly used as ultraviolet (UV) radiation stabilizers because of their ability to act as scavengers of free radicals. UV stability is very important to the plastics industry as minimal exposure to sunlight to degrade is highly undesirable for polymers. Therefore, additives for poly (4-methyl-1-pentene) that significantly increase the UV stability of polymers over that produced by either hindered amines alone or in known combinations with other compounds are well known in the art. Will make an important contribution.

Degradation is a major adverse condition that polymers undergo due to their long exposure to the environment. When polymers degrade, they generally lose strength and tend to crack. Thermally induced and / or promoted degradation can be minimized by using selected antioxidants. Although these measures have reached the stage of success, further improvements in either the methods and / or materials used are desired. Therefore, it would be an important contribution to the art to provide an additive composition that improves the thermal stability of polymers.

Once molded, the polymer is often pinch sealed to form the desired container. However, seals are often poorly formed due to polymer chemistry. An additive composition that would enhance the polymer's ability to fully pinch seal would be a significant contribution to the art.

[0009]

According to the present invention, poly (4-methyl-1-pentene) consisting of at least one hindered amine, at least one phosphite compound and optionally one or more hindered phenols. ) To provide an additive composition for improving the processing stability. The present invention also provides poly (4) containing the additive composition.
-Methyl-1-pentene) composition. Generally, the additive composition is also poly (4-methyl-1-pentene).
Increase the UV stability of.

The above additive compositions also contain poly (4) when they contain at least one hindered phenol.
-Methyl-1-pentene) to improve the thermal stability or pinch sealability.

The ratio of hindered amine to phosphite compound can range from about 0.1 to about 10: about 0.1 to about 10. The preferred ratio is about 1: 2. When hindered phenol is added, the ratio of hindered amine to phosphite compound to hindered phenol is from about 0.1 to about 1.
Each can range from 0: about 0.1 to about 10: about 0.1 to about 10. The preferred ratio is 1: 2: 1 respectively.

All hindered amines are generally considered useful in the practice of this invention. Compounds in this class include: (A) dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, (b) poly ((6-((1,1,3,3
-Tetramethylbutyl) -imino) -1,3,5-triazine-2,4-dyl) (2-3,2,6-6-tetramethylpiperidyl) -imino) -hexamethylene-
(4- (2,2,6,6-tetramethylpiperidyl))
-Imino)), (c) poly ((6-morpholino-s-
Triazine-2,4-dyl) (2,2,6,6-tetramethyl-4-piperidyl) imino) -hexamethylene (2,2,6,6-tetramethyl-4-piperidyl) imino), (d ) Bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, (e) poly (2,2,6,6-tetraalkyl-4-piperidyl) amine.

All phosphite compounds are believed to be very useful in the practice of this invention. Compounds in this class include: (A) bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, (b) bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite + triisopropylamine,
(C) tris-2,4-di-t-butylphenylphosphite, (d) bis (2,4-tris-t-butylphenyl) pentaerythritol diphosphite,
(E) Distearyl pentaerythritol diphosphite, and (f) tetrakis [2,4, di-t-
Butylphenyl] 4,4 'biphenylene diphosphite.

The addition of hindered phenolic compounds is optional when it is desired to improve processing stability and / or UV stability. The highest synergistic effect exists between the hindered amine combined with the phosphite, as the hindered phenol, when added together with the hindered amine and phosphite, contributes to the improvement of both process stability and UV stability. Additive compositions useful for improving thermal stability and pinch sealability include at least one hindered phenol in addition to the hindered amine and phosphite compound. All hindered phenols are also considered to be very useful in the practice of this invention. Compounds in this class include: (A) tetrakis (methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate))-methane,
(B) Octadecyl-3-5-di-t-butyl-4-
Hydroxyhydrocinnamate, (c) 1,3,5-Tris (3,5-di-t-butyl-4-hydroxybenzyl) -mesitylene, (d) 1,3,5-Tris (3,3
5-di-butyl-4-hydroxybenzyl) -isocyanurate, and (e) 1,3,5-tris (2-hydroxyethyl) -s-triazine-2,4,6- (1
3,5-di-t-butyl-4-hydroxyhydrocinnamic acid triester with (H, 3H, 5H) trione.

When the desired result is improved processing stability,
Preferred combinations of hindered amine and phosphite compounds are each present in a preferred ratio of 1: 2 4-
Hydroxy-2,2,6,6-tetramethyl-1-piperidine Ethanol dimethylsuccinate polymer and bis (2,4-di-t-butyl) pentaerythritol diphosphite. If any hindered phenol is added, the preferred addition is 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl).
-The addition of mesitylene. These compounds are 1: 2:
It is preferably present in each ratio of 1.

If the desired result improves UV stability, the preferred combinations of hindered amine and phosphite are present in 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine, each present in a preferred ratio of 1: 2. Dimethyl succinate polymer with ethanol and tris-2,4, di-t-butylphenyl phosphite. If any hindered phenol is added, the preferred addition is 1,3,5-tris (3,5-dibutyl-4-hydroxybenzyl) -isocyanurate. These compounds are preferably present in a respective ratio of 1: 2: 1.

If the desired result is improved thermal stability,
A preferred combination of hindered amine, phosphite compound and hindered phenol is dimethylsuccinate polymer and 4-bis-2,2,6,6-tetramethyl-1-piperidineethanol and bis (2,4-di-t-, respectively). Butyl) pentaerythritol diphosphite and tetrakis (methylene (3,5-
Di-t-butyl-4-hydroxyhydrocinnamate) methane. These compounds are preferably present in a respective ratio of 1: 2: 1.

Preferred combinations of hindered amines, phosphites and hindered phenols are the preferred combinations of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and dimethyl, respectively, if the desired result is improved pinch sealing. Succinate polymer, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and tetrakis (methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane and 1,3,3. There are two hindered phenols, 5-tris (3,5-dibutyl-4-hydroxybenzyl) -isocyanurate, these compounds being preferably 1 (hindered amine): 2 (phosphite): 1 (hindered phenol). ) Exist in each ratio.

When the polyolefin is combined with the above additives consisting of a hindered amine, a phosphite compound and optionally a hindered phenol, the resulting compound is mixed under suitable conditions for a time sufficient to obtain a homogeneous mixture.

In general, all polymers are useful in the practice of this invention. However, polyolefins including but not limited to poly (4-methyl-1-pentene), polypropylene and polyethylene are preferred. Poly (4-methyl-1-pentene) is the preferred compound of this field. Traditional additives are not intended to be limiting, but include antistatic agents, acid neutralizing agents, thioesters and nucleating agents as well as colorants that can also be used in the practice of the present invention.

The additive package of the present invention comprises at least 1 of each in an amount sufficient to provide the desired effect on the polyolefin, ie improved process stability and, if desired, UV stability, thermal stability or pinch sealability. Of one hindered amine, at least one phosphite compound and optionally one or more hindered phenols. Hindered amines, phosphites and hindered phenols are about 0.0001
To about 10.0 (wt / wt)% in a wide range of amounts, about 0.01 to about 1.0% (wt / wt)% in the preferred range, and about 0.05 to about 0.5. It can be present in the most preferred amount in the range of% (weight / weight).
However, the preferred amount of phosphite compound is about 0.0
Amounts range from 10 to about 1.0% (w / w), and the most preferred range is from about 0.05 to about 0.40% (w / w). Note that these weight percentages given here are based on the combined weight of poly (4-methyl-1-pentene) and of the additive package of the present invention.

The general method for improving the process stability of poly (4-methyl-1-pentene) by combining it with the additive package of the present invention, and if desired, UV stability or pinch sealing, is as follows. It consists of the steps described in.

The polymer is introduced into a suitable mixing vessel. Thereafter, a measurable amount of hindered amine, phosphite and optionally hindered phenol are introduced into the mixing vessel. The mixture containing the polymer and the additive package of the present invention is thoroughly mixed and extruded repeatedly. The extrudates can then be measured intermittently for each melt for melt flow (process stability).

The mixing of the ingredients to form the composition of the present invention can be accomplished by using any conventional method and equipment known in the art. Mixing can be done at any suitable temperature. Typical temperature changes to effect this mixing of the raw materials are about 250 ° C to 320 ° C. Note that elevated temperatures promote decomposition and are generally not useful in the practice of the invention.

Polymer residence time is also important in the practice of this invention. The residence time is not intended to be limited, but depends on many factors, including the speed of the screw and the 1 / d ratio where 1 / d is a length greater than or equal to the diameter of the screw. Residence time is directly proportional to screw speed and inversely proportional to the 1 / d ratio. Screw speeds that are generally useful in the practice of the present invention are from about 30 to about 100 revolutions per minute (rp).
The range is m). However, screw speeds of about 40-70 rpm are preferred.

The measurement of the melt flow rate indicates the processing stability of the polyolefin. The term process stability, as used herein, refers to the degree of change in melt index on repeated extrusions. Therefore, small changes in melt index are evidence of improved process stability. UV stability, as used herein, refers to the polymer's ability to resist exposure to UV radiation without meaningful fast degradation.

The term thermal stability, as used herein, refers to a polymer's ability to withstand long term exposure to thermal conditions without rapid degradation. The term pinch sealability, as used herein, refers to the ability of a molded polymer to maintain a pinch seal without splitting.

[0028]

EXAMPLES Mixing Additives and Polymers The procedures described below for mixing additives and polymers are relevant to all the Examples described below.

Polymethylpentene (PMP) fluff was weighed and mixed with the same amount of pre-prepared concentrate of polymethylpentene and additive formulation. The fluff and concentrate were added to a sealed polyethylene package and inserted into a 64 ounce wide mouth polypropylene bottle. The bottle was tumbled on a roll mill for 1 hour to thoroughly mix the polymer and additives. Polyethylene was inserted in place of the polypropylene bottle alone to reduce static sticking to the container wall and for better sample recovery.

[0030] Treatment below for push out Shi extrusion is related to Examples 1 to 6 The following implementing processability improved stability.

Polymethylpentene containing the additive formulation was 0.125 using a 0.75 inch Brabender single screw extruder with a length to width (L / D) ratio of 24.
Extruded from an inch stand die. Extrusion temperature is 40 ~
It was 260-310 ° C. at a screw speed of 50 RPM. Most of the extrusion was done at 300 ° C and 50 RPM. The extruded strands are chilled with water to 25-30 ° C. and then a Killian 2 inch rub (La).
b) Pelleted on a pelletizer. The pelletized samples were extruded into pellets a total of 3 times for each sample and 2 more times using the same conditions. A sample is taken from the raw material after each operation to measure the melt flow rate.

Ultraviolet (UV) Aging The procedures described below for testing UV stability are related to Example 7 below.

The sample was compression molded at 525 ° F. and 25 tons of force into a 5 × 5 inch × 20 mil sheet from which five 0.5 × 1.75 inch strips were cut. Place each of these strips on a weatherometer rack and place the atlas kissenone (Atlas X
aged in a weatherometer at 75 ° F.
The break was defined as the break when the strip was bent to 90 °. The time to failure was calculated by averaging the time to failure for each of the five strips.

The procedure described below for testing oven aging thermal stability is described in Example 8 below.
Related to. The sample was compression molded at 525 ° F. and 25 tons of force into a 5 x 5 inch x 20 mil sheet, and then five 0.25 x 1.75 inch strips were cut. Each of these strips was placed in an aging test tube in a Pyrex glass oven and placed in a forced air Blue (M) oven at 150 ° C.
Aged. The strip was randomly scattered from corner to corner of the oven and rotated to randomize possible hot spots in the oven. Fracture was defined as any yellowing, disintegration or other visual deterioration of the strip. The break time on the date is 5
The average time to failure for each individual strip was calculated.

Perfect Pinch Seam in Extrusion Blow Molding
The following procedure for testing pinch sealability is related to Example 9 below. This test was a pass / fail test. The seal was formed on the bottom of a blow molded bottle with the two pieces together. The seal does not form in a partial procedure, but generally does or does not seal. The integrity of the seal is determined by visual inspection or thumb pressure (10 to 25 pounds) on the seal line. If the seal was not good, pressing the seal line separated the two bottle pieces. If the seal was good, it was not separated.

Description of Tables The indication for the melt flow rate of the polymer after the third extrusion operation was divided by the melt flow rate of the polymer after the first extrusion operation. The polymethylpentenes used in these have an initial melt flow rate of 140 or higher divided by the melt index of 20 of the first operation. A melt index above 140 was difficult to measure accurately and was beyond the practical range for blow and injection molding applications, so an upper limit ratio of 7 was chosen.

The table shows the Roman number I showing the following chemical composition:
-Refer to XVI. Hindered amine I-4-hydroxy-2,2,6,6-tetramethyl-
Dimethyl succinate polymer with 1-piperidine ethanol, II-poly-((6-((1,1,3,3-tetramethylbutyl-imino) -1,3,5-triazine-2,4-dyl)) -2- (2,2,6,6-tetramethylpiperidyl) -imino-hexamethylene-4-
(2,2,6,6-tetramethylpiperidyl)-) imino)), III-poly (((6-morpholino-s-triazine-2,4-dyl) (2,2,6,6-tetra Methyl-4-piperidyl) imino-)-hexamethylene (2,2,6,6-tetramethyl-4-piperidyl) -imino), IV-bis (2,2,6,6-tetramethyl-4-piperidinyl) ) Sebacate, V-poly (2,2,6,6-tetraalkyl-4-piperidyl) amine, and phosphite compound VI-bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, VII -Bis (2,
4-di-t-butylphenyl) pentaerythritol diphosphite triisopropylamine, VIII-tris-2,4-di-t-butylphenylphosphite, IX-bis (2,4-tri-t-butylphenyl)
Pentaerythritol diphosphite, and X-distearyl pentaerythritol diphosphite, X
I-tetrakis [2,4 di-t-butylphenyl] 4,
4'biphenylene phosphonite. Hindered phenol XII-tetrakis (methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)) methane, XI
II-octadecyl-3-5-di-t-butyl-4-hydroxyhydrocinnamate, XIV-1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -mesitylene, XV -1,3,5-Tris (3,5
-Di-t-butyl-4-hydroxybenzyl) -isocyanurate, and XVI-1,3,5-tris- (2
-Hydroxyethyl) -5-triazine-2,4,6-
3,5-Di-t-butyl-4-hydroxyhydrocinnamic acid triester with (1H, 3H, 5H) trione

Example 1 Table 1 shows HALS (I) resulting in improved processing stability.
And phosphite (VII) synergy.

Table 1 Table 1 Synergy of (I) and Phosphite (VII) | Concentration of Additives% | Test VII I P3 / P1 Control AO None> 7.00 1 0.2> 7.00 2 0.1 > 7.0 3 0.2 0.1 2.49

Tables 2, 3 and 4 show HALS (I), Phosphite (VII and Irgafos (Irgafo).
s) VIII) and hindered phenols (XII,
XV, or XIV) synergism and improved processing stability. These results indicate that the HALS / phosphite combination is affected or absent with zinc stearate. These results also show that the effect of HALS / phosphite is enhanced by the presence of hindered phenol, that is the optimum effect is the result of the combination of the three additives, hindered phenol, phosphite and HALS. ing.

Example 2

[Table 2] Table 2 Synergy of HALS I, phosphite VIII and VII, and hindered phenol XV ｜ Additive concentration% ｜ Test XV VIII VII I Zn St P3 / P1 Control AO None> 7.00 1 0.1> 7.00 2 0.2> 7.00 3 0.2> 7.00 4 0.1> 7.00 5 0.1 0.1 4.29 6 0.1 0.2 3.43 7 0.1 0.2 0.2 0.1 1.78 8 0.1 0.2 2.91 9 0.1 0.2 0.1 2.06 10 0.1 0.2 0.1 0.05 1.92 11 0.1 0.2 0.1 0.05 2.20

Example 3

[Table 3] Table 3 Synergy of 622, phosphite VIII and VII , and hindered phenol XIV ｜ Additive concentration% ｜ Test XIV VIII VII I Zn St P3 / P1 Control AO None> 7.00 1 0.1> 7.00 2 0.2> 7.00 3 0.2> 7.00 4 0.1> 7.00 5 0.1 0.2 3.52 6 0.1 0.2 0.1 1.84 7 0.1 0.2 0.1 2.27 8 0.1 0.2 0.1 2.27

Example 4

[Table 4] Table 4 Synergy of HALS I, phosphite VIII and VII, and hindered phenol XII ｜ Additive concentration% ｜ Test XII VIII VII I Zn St P3 / P1 control No AO> 7.00 1 0.1> 7.00 2 0.2> 7.00 3 0.2> 7.00 4 0.1> 7.00 5 0.1 0.2 2.30 6 0.1 0.1 2.47 7 0.1 0.2 0.1 0.05 2.13 8 0.1 0.2 0.1 0.05 2.07

Example 5 Table 5 shows the effect of the presence of zinc stearate. These data indicate that zinc stearate does not enhance the effectiveness of the additive package. In general, despite the presence of stearic acid, it does not affect the process stabilization performance of the additive package. Zinc stearate appears to have a detrimental effect, but with phosphite and / or
Or zinc in the presence of HALS never improves processing stability. The improvement in processing stability is due to the synergistic effect of the phosphite-HALS interaction.

[Table 5] Table 5 Effect of zinc stearate ｜ Additive concentration% ｜ Test XV XIV XII VIII VII I Zn St P3 / P1 Control AO None> 7.00 1 0.1> 7.00 2 0.1 0.05 3.81 3 0.1 0.1 4.29 4 0.1 0.1 0.05 4.69 5 0.1 0.2 0.1 2.06 6 0.1 0.2 0.1 0.05 2.20 7 0.1 0.2 0.1 1.96 8 0.1 0.2 0.1 0.05 1.92 9 0.1 0.2 0.1 2.92 10 0.1 0.2 0.10 4.30 11 0.1> 7.00 12 0.1 0.05 3.93 13 0.1 0.1 2.50 14 0.1 0.1 0.05 5.19 15 0.1 0.2 0.1 1.84 16 0.1 0.2 0.1 0.05 2.27 17 0.1 0.1 2.47 18 0.1 0.1 0.05 3.75

Example 6 Table 6 shows that the above modifications are based on thioesters (DLTDP), zinc stearate and other hindered phenols (XII).
It shows that it is still retained in the presence of various combinations of additives such as I).

[Table 6] Table 6 Synergistic effect in the presence of additive formulation ｜ Additive concentration% ｜ Test XII XIII XIV XV DLTDP VII I ZnSt P3 / P1 Control AO None >>. 0 1 0.05 0.05 0.20 0.05 6.33 2 0.05 0.05 0.20 0.20 1.79 3 0.05 0.05 0.20 0.05 1.80 4 0.05 0.05 0.20 0.20 1.71 5 0.05 0.05 0.20 0.05 4.27 6 0.05 0.05 0.20 0.20 1.86 7 0.10 0.10 0.10 0.10 1.71 8 0.10 0.10 0.10 0.10 2.13 9 0.10 0.10 0.10 0.10 2.00 10 0.10 0.20 0.05 3.49

Example 7

[Table 7] Table 7 XII XV VIII I ZN ST UV Aging HRS 0.1 0.2 0.1 1280 0.1 0.2 0.1 1280 0.1 0.1 0.05 843 0.1 0.1 0.1 843 0.1 666 0.1 0.1 0.05 621 0.05 528 ──────────── ──────────────────────── 0.1 0.2 0.1 1267 0.1 0.1 0.05 843 0.1 0.2 0.1 474 No additive 333

By the synergistic effect of Table 7 on the UV aging from the combination of phosphite and hindered amine light stabilizers, the effect of the combination of HALS (I) and phosphite (VIII), these two components being the other It can be explained that longer UV aging times are obtained than when used without.

Since the packages with the best performance do not contain zinc stearate, problems can arise as to whether zinc stearate reduces the performance of the additive package. Zinc stearate does not reduce the performance of the package.
As the table shows, the UV aging of the resin containing only zinc stearate was better than the resin without any additives (528 h-333 h). In the presence of hindered phenol (XII) and HALS (I), 0.05-
Increasing the zinc stearate level of 0.10% had no effect on UV aging (843 hours in either case). The improved UV aging performance can be attributed to the effect from the presence of the VIII and I blends.

Example 8 In Table 8, the control is the comparative resin Mitsui RT-
It was 18. The Phillips used
ps) resin has a nominal melt flow rate of 20% 1.8%
Was a decene copolymer. Mitsui RT-1
8 resin is 1.8% decene copolymer with a nominal melt flow of 20. The table shows that an oven aging stability equal to or better than our comparatives can be achieved with phosphite (VII) + HALS (I) and additive formulations containing various hindered phenols and other antioxidants. Explaining that. The performance of these additive formulations is better than our inventive package, the last row of the table.

[Table 8]

Example 9

[Table 9] Table 9 PTC blow molding test I Additive package XII XIV XV XIII VII VIII XI DLTDP I Zn St Pinch seal formation ^* 0.05 0.05 0.2 0.2 Yes 0.05 0.05 0.2 0.2 None 0.05 0.05 0.3 0.05 None 0.05 0.05 0.2 0.2 None 0.1 0.1 0.2 0.1 Yes 0.05 0.05 0.2 0.1 No 0.05 0.05 0.2 0.1 0.05 No 0.1 0.1 0.1 No 0.07 0.14 0.2 0.1 No 0.1 0.2 0.1 No 0.1 0.2 0.04 No 0.1 0.08 No

[Table 10] Table 10 PTC blow molding test I Additive package XII XIV XV XIII VII VIII IX DLTDP I Zn St Pinch seal ^{* *} (DHT formation 4A) 0.1 0.2 0.1 Yes 0.1 0.1 0.1 0.1 Yes 0.1 0.2 0.1 Yes 0.1 0.1 0.1 0.1 Yes 0.05 0.05 0.2 0.1 Yes 0.1 0.1 0.1 0.1 Yes 0.05 0.05 0.2 0.1 Yes 0.1 0.1 0.2 0.1 Yes 0.1 0.2 0.1 ^* (0.05) Yes 0.05 0.05 0.2 0.1 Yes 0.05 0.05 0.2 0.2 Yes 0.1 0.1 0.2 0.1 Yes 0.05 0.05 0.2 0.2 0.04 Yes 0.1 0.2 0.04 No

Claims (15)

[Claims] 1. A mixture of at least one hindered amine and at least one phosphite compound, wherein the hindered amine to phosphite ratio is about 0.
1 to about 10: in the range of about 0.1 to about 10, wherein the hindered amine is 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol in dimethylsuccinate polymer, poly-((6 -((1,1,3,3-Tetramethylbutyl-imino) -1,3,5-triazine-2,4-dyl) -2- (2,2,6,6-tetramethylpiperidyl)- Imino-hexamethylene-4-
(2,2,6,6-tetramethylpiperidyl) -imino)), poly ((6-morpholino-s-triazine-
2,4-Dill) (2,2,6,6-tetramethyl-4
-Piperidyl) imino-)-hexamethylene (2,
2,6,6-Tetramethyl-4-piperidyl) imino), bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, or poly (2,2,6,6-).
Tetraalkyl-4-piperidyl) amine, and the phosphite compound is bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol di Phosphite + triisopropylamine, tris-2,4-di-t-butylphenyl phosphite,
Bis (2,4-tri-t-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, or tetrakis [2,4
4-methyl-, characterized in that it is di-tert-butylphenyl] 4,4 'biphenylene diphosphite
1-Additive composition for increasing the processing stability of pentene polymers. 2. The hindered amine is a dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol and the phosphite is bis (2,4-di-t-). A composition according to claim 1 which is butylphenyl) pentaerythritol diphosphite, and wherein said ratio of said hindered amine to said phosphite is 1: 2. 3. The hindered amine is a dimethylsuccinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, and the phosphite is tris-2-4, di-t-. A composition according to claim 1 which is butyl phenyl phosphite, wherein said ratio of said hindered amine to said phosphite is 1: 2 and increases the UV stability of the polymer of 4-methyl-1-pentene. 4. Tetrakis (methylene (3,5-di-t
-Butyl-4-hydroxyhydrocinnamate)) methane, octadecyl-3,5-di-t-butyl-4-hydroxyhydrocinnamate, 1,3,5-tris (3,5
-Di-t-butyl-4hydroxybenzyl) -mesitylene, 1,3,5-tris (3,5-di-t-butyl-4)
-Hydroxybenzyl) -isocyanurate, or 1,
3,5-Di-t-butyl-4-hydroxyhydrocinnamic acid tris with 3,5-tris- (2hydroxyethyl) -5-triazine-2,4,6- (1H, 3H, 5H) trione Comprising at least one hindered phenol which is an ester, wherein the ratio of the hindered amine to the phosphite to the hindered phenol is about 0.1 to about 10: about 0.1 to about 10: about 0.1 to about 10.
A composition according to any one of claims 1 to 3 in the range of. 5. The at least one hindered phenol is 1,3,5-tris (3,5-di-t-butyl-).
A composition according to claim 4, which is 4-hydroxybenzyl) mesitylene, and wherein the ratio of the hindered amine to the phosphite to the hindered phenol is 1: 2: 1. 6. The at least one hindered phenol is 1,3,5-tris (3,5-dibutyl-4-hydroxybenzyl) -isocyanurate, the hindered amine vs. the phosphite vs. the hindered phenol. Said ratio of 1: 2: 1, 4-methyl-
A composition according to claim 4, which increases the UV stability of the polymer of 1-pentene. 7. The hindered amine is a dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol and the phosphite is bis (2,4-di-t-). Butylphenyl) pentaerythritol diphosphite, and the hindered phenol is tetrakis (methylene (3,3
5-di-t-butyl-4-hydroxyhydrocinnamate)) methane and said ratio of said hindered amine to said phosphite to said hindered phenol is 1: 2: 1 and 4-methyl-1- A composition according to claim 4, which increases the thermal stability of the pentene polymer. 8. The hindered amine is a dimethylsuccinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, and the phosphite is bis (2,4-di-t-). Butylphenyl) pentaerythritol diphosphite, and the hindered phenol is tetrakis (methylene (3,3
5-di-t-butyl-4-hydroxyhydrocinnamate)) methane and 1,3,5-tris (3,5-di-
t-butyl-4-hydroxybenzyl) -mesitylene and a pinch of a polymer of 4-methyl-1-pentene, wherein the ratio of the hindered amine to the phosphite to the hindered phenol is 1: 2: 1. A composition according to claim 4, which increases the sealing properties. 9. A composition comprising poly (4-methyl-1-pentene) and an additive composition according to any one of the preceding claims 1-8. 10. The hindered amine is about 0.000.
The phosphite compound is present in the composition in an amount ranging from 1% (w / w) to about 10.0% (w / w), the phosphite compound being poly (4-methyl-1-pentene) and an additive composition. Approximately 0.0001% (weight /
A composition according to claim 9 which is present in an amount ranging from (weight) to about 10.0% (weight / weight). 11. The hindered amine is about 0.01 to.
Present in an amount in the range of about 1.0% (weight / weight), wherein the phosphite compound is about 0.01 to about 1.0% (weight / weight).
A composition according to claim 10 present in an amount in the range of (by weight). 12. The hindered amine is from about 0.05 to.
The composition according to claim 11, wherein the composition is present in an amount in the range of about 0.5% (w / w) and the phosphite compound is present in an amount in the range of about 0.05 to about 0.50% (w / w). object. 13. The hindered phenol is about 0.0.
001% (weight / weight) to about 10.0% (weight / weight)
A composition according to any one of claims 9 to 12 present in an amount in the range of. 14. The hindered phenol is about 0.0.
14. The composition according to claim 13, which is present in an amount ranging from 1 to about 1.0% (weight / weight). 15. The hindered phenol is about 0.0.
The composition according to claim 14, which is present in an amount ranging from 5 to about 0.5% (weight / weight).