AU694864B2 - Introduction of long chain branching into linear polyethylenes - Google Patents

Description

-1- INTRODUCTION OF LONG CHAIN BRANCHING INTO LINEAR POLYETHYLENES The invention relates to altering linear polyethylenes to provide them with long chain branching. The invention realtes to a product produced by a process comprising contacting a linear polyethylene with a peroxide and a solid antioxidant in the presence of nitrogen to introduce long chain branching into the linear backbone of linear polyethylenes.

The process of the invention provides a method of crosslinking resins in the presence of both primary and secondary antioxidants in a single step. The :use of a nitrogen blanket significantly improves the efficiency of the high temperature peroxide. The results include high increase in viscosity, as measured by 12, or dynamic viscosity, at significantly low levels of peroxide.

This process can be implemented over a wide range of compounding 15 equipment with a variety of polyethylene resins produced by Ziegler, chromium or metallocene catalyst.

In one aspect the present invention provides a process for introducing long chain branching and for crosslinking an uncrosslinked polymer of ethylene or copolymer of ethylene and an alpha olefin of 3 to 10 carbon atoms, S 20 comprising: I, admixing a base resin comprising an uncrosslinked polymer of ethylene or copolymer of ethylene, antioxidants and high temperature peroxide, which has a half life temperature at 0.1 hours which is greater than 130 0 C, in an inert atmosphere at the feed throat of the extruder, at a melt temperature of 180-300 0 C, wherein the amount of high temperature peroxide is 10-1000 ppm wherein the total amount antioxidants is 100-3000 ppm; allowing increase in the numerical value of 12I/12 [measured at 190 0 C, according to ASTM 1238], of 15-500% over base resin, a decrease in the 12 numerical value of 15-500% over base, and increase in the dynamic viscosity [measured ASTM D4440-84] of 25-1000% over base resin; recovering a product which contains long chain branching.

O VAT:C:\Winword\Vlolet\NeiRNodelete\53697-96.doc 1 ~of/b -la- In accordance with the invention, the untreated uncrosslinked polyethylene is contacted with a peroxide and an antioxidant under a nitrogen blanket at the feed hopper at a temperature of 180-3000C. The amount of the antioxidant will range from 100 to 3000 ppm based on the blend of HDPE, antioxidants and peroxide.

The LLDPE is compounded with primary and secondary am. ,xidant.

The role of antioxidant stabilizers in polyethylene is to protect the polymer from oxidative degradation after compounding and thus preserve its strength properties. The mechanism for degradation of polyethylene via oxidation is an autocataiyzed, free radical chain process. During this process hydroperoxides are formed which decompose into radicals and accelerate the degradation.

Antioxidants prevent this degradation by scavenging radicals to interrupt the oxidative chain reaction resulting from hydroperoxide decomposition and (2) consuming hydroperoxides.

t I 1 t 4 VAT:C\Winword\Vtolet\NeiNodelet.~, zq6 3CC.a r i WO 96133226 PCTIUS96/03959 2 The primary antioxidants contain one or more reactive hydrogen atoms which tie up free radicals, particularly peroxy radicals, forming a polymeric hydroperoxide group and relatively stable antioxidant species. The phenolic antioxidants are the larges selling primary antioxidant used in plastics today; they include simple phenols, bisphenols, thiobisphenols, and polyphenols. Hindered phenols such as Ciba Geigy's Irganox 1076, 1010, and Ethyl 330 fulfill the first requirement and are considered primary antioxidants. Others include: 2,6-Bis(l-methylheptadecyl)-p-cresol Butylated hydroxyanisole [BHA], [(CH 3 3

CC

6

H

3

OH(OCH

3 Butylated hydroxytoluene [BHT], [DBPC], [Di-t-butyl-pcresol] Butylated octylated phenol 4,4'-Butylidenebis(6-t-butyl-m-cresol) [Santowhite powder] 2,6-Di-t-butyl methylamino-p-cresol hydroxy-cinnamate) IIrganox 259] 2,2'-Methylenebis(4-methyl-6-t-buty phenol) [CAO [Bis(2-Hydroxy-3-t-butyl-5-methy phenyl)methane], [Cyanox 2246] Octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate [Irganox 1076] Tetrakis(methylene(3,5-di-t-butyl-4hydroxyhydrocinnamate)methane [Irganox 1010] 4,4'-Thiobis(6-t-butyl-m-cresol) [Santonox] Thiodiethvlenebis(3,5-di-t-butyl-4-hydroxy)hydrocinnamate [Irganox 1035] 1,3,5-Tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)1,3,5triazine-2,4,6-(1H, 3H, 5H)-trione [Cyanox 1790] Tris(2-methyl-4-hydroxy-5-t-butylphenyl)-butane [Topanol

CA]

PROPRIETARY PHENOLICS Antioxidant MBP-5P, Antioxidant SP i i; j WO 96/33226 PCTfUS96/03959 3 Antioxidant TBE-9 Antioxidant TBM-6P, 6T [Thiophenol] CAO-42 Escoflex A-122, A-123 Hostanox 03 Isonox 129 (bisphenolic] MO-14 Naugard 431 [hindered phenolic] Naugard XL-1 Prodox 120 Prodox 147 Prodox 247 Prodox 340, 341, 343 Prodo B11 Prodox B121 Stabilite 49-467, 49-470 Uvi-Nox 1492 Vanox GT Vanox SKT

J

Vanox 1290, 1320 Wingstay C Wingstay L [polymeric hindered phenol] Wingstay S [styrenated phenol] IWingstay

T

Wingstay V Naugard P, PHR Weston 399 430 Weston 626 Weston 430, 474, 491, 494, DHOP, PTP, PNPC, THOP Tetrakis (2 ,4-di-t-butyl) phenyl- 1-bi-phenyl) -4,4 diylbisphosphite (Sandostab P-EPQ] Triisodecyl phosphite [Weston TDP] Triisooctyl phosphite [Weston TIOP] TriLauryl phosphite (Weston TLP] Trisnonylphenyl phosphite 4A SWO 96/33226 PCT/US96/03959 4 Didecyl phosphite Di Lauryl phosphite [(C 12

H

29 0) 2

PHO]

Trisnonylphenyl phosphite/formaldehyde polymer [Wytox 438] Wytox 320 (alkylaryl phosphite) The major group of secondary antioxidants include phosphorus-based antioxidants, generally phosphites. The phosphite acts by converting hydroperoxides to non-chain propagating alcohols, while the phosphite itself is oxidized to phosphates. These additives are chosen when processing stability is of concern. Trisnonylphenyl phosphite is the most widely used phosphite. Typical secondary antioxidants are GE's Weston TNPP, Ciba Geigy's Ultranox 626 and Irgafos 168. An exhaustive list of primary and secondary antioxidants can be found in the reference [Chemical Additives for the Plastics Industry, Radian Corporation, Noyes Data Corporation, NJ, 1987.] Others include: Tetrakis(2,4-di-t-butyl)phenyl-(l,1-bi-phenyl)-4,4'diylbisphosphite [Sandostab P-EPQ]; Triisodecyl phosphite [Weston TDP]; Triisooctyl phosphite [Weston TIOP]; TriLauryl phosphite [Weston TLP]; Trisnonylphenyl phosphite; Didecyl phosphite; Di Lauryl phosphite [(C 2

H

29 0) 2

PHO];

Trisnonylphenyl phosphite/formaldehyde polymer [Wytox 438]; and Wytox 320 (alkylaryl phosphite).

In accordance with the invention, the mixture of primary antioxidant and secondary antioxidant in the LLDPE may comprise up to 3000 ppm of the blend.

Preferably, the antioxidant is a solid at ambient conditions.

The amount of peroxide will range from 10 to 1000 ppm based on the blend of HDPE, antioxidant and peroxide.

Ir L-Y I WO 96/33226 PCTUS96/03959 However, preferably, the peroxide amount ranges from 10 to 500 based on the PE weight. Most preferably, the peroxide of the blend is 10-300 ppm.

The types of peroxides which are used are high temperature peroxides that can undergo almost complete decomposition at normal compounding temperatures (200- 2600C). The half life temperature at 0.1 hours should be greater than 1300C. Half life temperature at a given time is the temperature at which one half of the peroxide has decomposed. Suitable but non-limiting examples of such peroxide are: dicumyl peroxide, 2,5-dimethyl-2,5-di-(tert butyl peroxy) hexane, tert-butyl cumyl peroxide, di-(2tert-butylperoxy-isopropyl) benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, cumene hydroperoxide these contain 2 to 20 carbon atoms.

The peroxide may be pre-blended with the PE or introduced separately as a liquid feed using any of various methods known in the art.

Treatment of the polyethylene must be undertaken under nitrogen. Nitrogen will be introduced to the zone of polyethylene treatment in accordance with the invention at the feed throat of the compounding extruder so as to minimize exposure to oxygen. Compounding under this condition significantly enhances the crosslinking efficiency of the peroxide.

The polyethylene employed as the reactant to be treated in accordance with the invention may be either high density polyethylene, sometimes designated by the acronym "HDPE", or linear low density polyethylene sometimes designated by the acronym "LLDPE". The HDPE will have a specific gravity of 0.94 to 0.97 g/cc whereas the LLDPE will have a specific gravity of 0.89 up to 0.94 g/cc.

Accordingly, polyethylenes which can be used herein will have a density in the range of 0.89 to 0.97 [ASTM D-1505].

These linear polyethylenes have a substantially linear r WO 96/33226 PCT/US96/03959 6 backbone and contain substantially no long branching.

Accordingly, the reactant polyethylene may be either a homopolymer of ethylene or a copolymer of ethylene and an alpha olefin of 3 to 10 carbon atoms preferably an alpha olefin of 4 to 10 carbon atoms. Preferred monomers include an olefin, preferably a 1-olefin, containing 3 to 10 carbon atoms, 1-propene, 1-butene, 1-pentene, 1-hexene, 4methyl-l-pentene, 1-heptene, and 1-octene. The preferred olefin comonomers are 1-butene, 1-hexene and 1-octene; when the polyethylene resin contains comonomers the resin will contain at least 80 preferably at least 90 mole percent ethylene units. The process of the invention can be implemented over a wide range of polyethylene resins produced by Ziegler, chromium or metallocene catalysts, as indicated by the Examples below.

The polyethylene employed as the reactant to be treated usually has less shear thinning (dependence of viscosity on shear rate) than the peroxide treated product of the invention. The MFR [which is the ratio 2In/12 measured according to ASTM D-1238 conditions E for I2 and F for I21] is a reflection of shear thinning; shear thinning appears to increase with increasing numerical value of MFR.

The polyethylene employed as the reactant to be treated has a lower dynamic viscosity than the product realized by the process of the invention. The dynamic viscosity is measured at 190 0 C using dynamic melt rheometers as outlined in ASTM D4440-84. The increase in viscosity is based on that of the untreated LLDPE.

The polyethylene employed as the reactant in the process of the invention has a higher I2 than the product of the process. That is, the effect of the process of the invention is to decrease the 12 of polyethylene. Since I2 is inversely related to the low shear rate viscosity [ASTM D-1238 Condition E] of the resin, the decrease in 12 reflects the increase in viscosity as a result of peroxide 7 I. .IY-Cm WO 96/33226 PCT/US96/03959 use. The significantly larger decrease in 12 with the nitrogen blanket (sample B, Example 1) illustrates the increased crosslinking efficiency of the peroxide in the presence of a nitrogen blanket.

The product polyethylenes, whether hompolymers or copolymers, will contain long chain branching. The presence of long chain branching will significantly increase the low shear viscosity of the polyethylene. This increase in viscosity translates into higher melt tension during stretching of the PE melt. The increased melt tension allows for the PE to be used in applications which were not readily possible before, such as sheet extrusion, high stalk film blowing, foaming and blow molding.

The presence of long chain branching in the products of the invention, produced by the process of the invention, is indicated by the sharp increase in low shear rate viscosity, decrease in 12 and increase in MFR when compared to the base resin. In accordance with the invention, the amount of long chain branching which can be introduced can be measured in terms of the changes in these properties.

Most Broad Preferred Preferred Property Range Range Range Increase in Dynamic 25- 25-500% 50-300% Viscosity at 0.1 1000% frequency over base Decrease in I2 over 15- 20-200% 25-100% base 500% Increase in MFR 15- 20-200% 25-100% over base 500% The process of the invention can be implemented over a wide range of compounding equipment with a variety of polyethylene resins, both homopolymers and copolymers of a density in the range of 0.89 to 0.97, produced by Ziegler,

B

i t as, WO 96/33226 PCT/US96/03959 8 chromium or metallocene catalyst, as indicated by the Examples below. Also, while nitrogen is used to provide an inert atmosphere at the feed throat of the extruder, any I other inert (non-oxidizing) gases could also be utilized.

EXAMPLES

Example 1 Granular LLDPE MI, nominal .918 density 1-hexene copolymer) resin produced with a Ziegler catalyst is mixed in with 500 ppm Irganox 1010 and 500 ppm of Irgafos 168.

We studied the effect of peroxide addition and a nitrogen blanket i, the feed hopper during compounding. We used Trigonox 101 E5 (supplied by Akzo) a 5 percent solution in mineral oil for these experiments. The peroxide was added as a 1 percent masterbatch in a granular LLDPE resin. The mixtures were compounded on a laboratory 3/4" Brabender twin screw extruder at 220 0 C and 25 RPM. The following table illustrates the influence of peroxide and nitrogen blanket: Ii ~i; 25 Peroxide Nitrogen Sample Level Blanket 12 121/12 Decrease Increase ppm_ in 12 in 121/1I A 0 Yes .89 24.7 B 100 Yes .26 53.6 70.8 117 C 100 No .55 35.3 38.2 42.9 The significantly larger decrease in 12 with the nitrogen blanket (sample B) illustrates the increased crosslinking efficiency of the peroxide in the presence of a nitrogen blanket. Since 12 is inversely related to the low shear rate viscosity of the resin, the decrease in 12 reflects the increase in viscosity as a result of peroxide use.

Sfi Q~aamt-WM--m-- ill i

I

-r WO 96/33226 PCTUS96/03959 9 Example 2 The compounding conditions were similar to those used in Example 1. The only changes were that a HDPE (.58 MI, nominal .953 density 1-hexene copolymer) polymerized with a chromium oxide catalyst was used as a feedstock instead of the LLDPE and with no secondary antioxidant. Only 500 ppm of Irganox 1010 was used. The results were as follows: Peroxide Nitrogen Sample Level Blanket 12 121/ Decrease Increase ppm _I 12 in 12 in T /I, D 0 Yes .058 72.4 E 100 Yes .09 213 84.5 194.2 F 100 No .24 128 58.6 76.8 Similar to Example 1, the sample with the nitrogen blanket gave a substantially larger decrease in 12 (or an increase in viscosity). The use of nitrogen blanket increases the crosslinking efficiency of the peroxide.

Example 3 This example illustrates the importance of selecting the proper secondary antioxidant to enhance the crosslinking efficiency of the peroxides. The compounding conditions were similar to that employed in Example 1, except for a different LLDPE feedstock MI, .918 density 1-hexene copolymer) and all samples had a nitrogen blanket on the feed throat of the hopper. The primary antioxidant Irganox 1010 was present at 500 ppm and the selected secondary antioxidant (phosphite) was also at 500 ppm.

_I WO 96/33226 PCT/US96/03959 Peroxide Secondary Decrease Increase Sample Level ppm Antioxidant 12 121 in 12 in I21/I 2 /12 G 0 Irgafos .8 27 168 H 100 Weston 399 .6 31. 25 17 6 I 100 Irgafos .29 48. 63.8 54.7 ___168 9 Comparison of Samples H and I, suggests that the choice of the secondary antioxidant has an important bearing on the efficiency of the peroxide crosslinking (measured by percentage of 12 decrease). Weston 399 which is a liquid at room temperature is dispersed quite effectively and curtails the crosslinking efficiency of the radicals generated by the peroxide. Irgafos 168 which is a solid (melting point 180-185 0 C) does not disperse as fast and thus allows the peroxide radicals to participate in the crosslinking of the polyethylene molecules. Thus solid antioxidants are preferred in this invention.

Example 4 In this example, we illustrate the use of the invention process in introducing low levels of long chain branches in a metallocene catalyzed LLDPE resin. We used a base LLDPE metallocene catalyzed (1-hexene copolymer) LLDPE granular resin with a 12 (MI) of 121/12 of 17 and a nominal density of .917. The granular LLDPE was preblended with 100 ppm of peroxide (used as granular masterbatch) 500 ppm Irganox 1010, and 500 ppm of Irgafos 168. The mixture was compounded on the 2 inch Brampton single screw extruder at 75 lbs/hr at 465 0 F with a nitrogen blanket at the feed throat. The resultant pelletized LLDPE (sample J) had the following properties:

$I

WO 96/33226 PCT/US96/03959 11 12 .44 121/12 23 Percentage decrease in 12 Percentage increase in I21/I2 Percentage increase in dynamic viscosity at .1 sec-i @1900C 122.5%. The percentage increase in viscosity was measured relative to the base untreated granular LLDPE resin. Dynamic viscosity is measured by a procedure described in ASTM D4440-84.

The presence of long chain branching is indicated by the sharp increase in low shear rate viscosity, decrease in 12 and increase in MFR when compared to the base metallocene catalyzed LLDPE resin.

Example In this example, we illustrate a large scale method of implementing the invention process. We used the 4 inch Farrel compounder for the purpose. 500 ppm of Irganox 1010 and 500 ppm Irganox 168 were dry-blended with the base LLDPE (nominal .65 MI, .922 density 1-hexene copolymer, In2/12 of 27, dynamic viscosity at .1 sec-i measured at 190°C of 123,200 poises). Instead of using a peroxide granular masterbatch described in the previous examples, we injected the 5% Trigonox solution in mineral oil (supplied by Akzo) directly into the Farrel mixer chamber. The flow rate of the peroxide solution was adjusted to obtain the desired level in the final polymer. Full nitrogen flow was employed on the hopper. The compounding rate was 550 lbs/hr with the specific energy input (SEI) of 0.11 (hp.hr)/.Lb. The melt temperature in the mixer was approximately 460 0 F. We obtained the following results: i f *4 t: ~4 *4

S

Perox- 12 121/ 12 Viscosity% Samyle Ide 112 1Decrease gI. I/see Viscosity Increase [Level J poises~i) Increase in I,/I, K 1 00 .261 46 601 369,500 200 150 .14 70 78.5 j 630,400 412 160 The dynamic viscosity is measured at 190 0 C using dynamic melt rheometers as outlined in ASTM D4440-84.

The increase in viscosity is based on that of the untreated LLDPE.

The invention process provides a highly effective means of modifying the base polyethylene even at the low levels of 100 ppm of the peroxide and in the presence of both the primary and secondary antioxidants.

Thus it is apparent that there has been provided, in accordance with the invention, a process and product, that fully satisfies the objects, aims, and advantages set forth above. While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims.

Throughout the description and claims of the specification the word "comprise" and variations of the word, such as "comprising" and "comprises", is not intended to exclude other additives, components, integers or steps.

Claims (3)

1. A process for introducing long chain branching and for crosslinking an uncrosslinked polymer of ethylene or copolymer of ethylene and an alpha olefin of 3 to 10 carbon atoms, comprising: admixing a base resin comprising an uncrosslinked polymer of ethylene or copolymer of ethylene, antioxidants and high temperature peroxide, which has a half life temperature at 0.1 hours which is greater than 1300C, in an inert atmosphere at the feed throat of the extruder, at a melt temperature of

180-3000C, wherein the amount of high temperature peroxide is 10-1000 ppm wherein the total amount antioxidants is 100-3000 ppm; allowing increase in the numerical value of ,21/I2 [measured at 1900C, according to ASTM 1238], of 15-500% over base resin, a decrease in the 1, numerical value of 15-500% over base, and increase in the dynamic viscosity [measured ASTM D4440-84] of 25-1000% over base resin; recovering a product which contains long chain branching. 2. A process according to claim 1, wherein the uncrosslinked homopolymer or copolymer has a specific density of 0.89 up to 0.97. 3. A process according to claim 1 or claim 2 wherein the antioxidants are solid at room temperature. 4. A process according to any one of the preceding claims wherein the uncrosslinked PE is produced by the use of Ziegler, chromium based or metallocene catalysts and mixtures thereof. A product produced by the process of claim 1. 6. A product produced by the process of claim 2. 7. A product produced by the process of claim 3. lei\Nodelete\53697-96.doc E~ P~ I -14- 8. A process according to claim 1 substantially as hereinbefore described with reference to any of the examples. DATED: 24 February, 1998 PHILLIPS ORMONDE FITZPATRICK Attorneys for: MOBIL OIL CORPORATION r s r r r r 1 r it rtrr I 1 :_YIIYI--..I i i ~_il i _Lili -/IIIIIUUI INTERNATIONAL SEARCH REPORT International application No. PCT/US96/03959 A. CLASSIFICATION OF SUBJECT MATTER IPC(6) :C08F 8/00 US CL :525/333.8, 387 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) U.S. 525/333.8,387 Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. Y US 5,405,917 A (MUELLER, JR., ET AL) 11 April 1995, 1-7 column 2. A US 4,578,431 A (SHAW ET AL) 25 March 1986. 1-7 A US 4,226,905 A (HARBOURNE) 07 October 1980. 1-7 A US 4,202,790 A (STELLER) 13 May 1980. 1-7 A US 4,015,058 A (SCHOBER) 29 March 1977. 1-7 A US 4,006,283 A (MACKENZIE, JR., ET AL) 01 February 1-7

1977. S Further documents are listed in the continuation of Box C. See patent family annex. S Special categories of cited documents: "T later document publihaed after the international filing date or priority date and not in conflict with the application but cited to understand the documentdefining the general state of the at which is not considered principle or theory underlying the invention to be of particular relevance SX' document of particular relevance; the claimed invention cannot be E' earlier document published on or after the international fihg date considered novel or cannot be considred to involve an inventive step document which may throw doubts on priority claim(s) or which is when the document is taken alone cited to establish the publication date of another citation or othernt of particur revance; the c invention cannot be specialmon (M pecified) document of particular relevance; the claimed invention cannot be special raon (as spcified) considered to involve an inventive step when the document is document referring to an oral disclosure, use, exhibition or other combined with one or more other such documents, such combination means being obvious to a person skilled in the at document published prior to the international filing date but later than document ma eber of the same patent family the priority date claimed Date of the actual completion of the international search MAY 1996 Date of mailing/of the international search report /A 2 JUL 1996/7 Name and mailing address of the ISA/US Commissioner of Patents and Trademarks Box PCI WashingtJn, D.C. 20231 Facsimile No. (703) 305-3230 Form PCT/ISA/210 (second sheet)(July 1992)*