THI NA TO DA UN AMIHA UNA MIRA

US009873782B2

(12) United States Patent ( 10 ) Patent No.: US 9 ,873,782 B2

Cottle et al. (45) Date of Patent: Jan . 23, 2018
(54 ) BIMODAL HIGH - DENSITY POLYETHYLENE ........................................ 525 / 53 , 240 , 333 . 8
RESINS AND COMPOSITIONS WITH See application file for complete search history .
IMPROVED PROPERTIES AND METHODS
OF MAKING AND USING THE SAME ( 56 ) References Cited
(71 ) Applicant: INEOS Olefins & Polymers USA , a U . S . PATENT DOCUMENTS
division of INEOS USA LLC , League 2007 /0276111 A1† 11/ 2007 Goldberg
City, TX (US) 2008 / 0097054 Al * 4 / 2008 Amos ................... C08F 210/16
526 / 135
(72 ) Inventors: Joshua Allen Cottle , Houston , TX 2008 /0161526 A11 7 / 2008 Guenther
(US ); Mark Anthony Gessner , 2009 /0088534 AL 4 /2009 Scheie et al.
Houston , TX (US ); Robert Ernest 2011 /0174413 A1† 7 / 2011 Ashbaugh
Sander , Houston , TX (US) ; Luc 2012 /0302681 A1 * 11/2012 Neubauer
Dheur, Brussels (BE ) FOREIGN PATENT DOCUMENTS
(73 ) Assignee: INEOS OLEFINS & POLYMERS WO 2014 /126839 Al † 8/ 2014
USA , a division of INEOS USA LLC ,
League City, TX (US ) OTHER PUBLICATIONS
( * ) Notice: Subject to any disclaimer, the term of this Notification Concerning Transmittal of International Preliminary
patent is extended or adjusted under 35 Report on Patentability (Chapter 1 of The Patent Cooperation
U . S . C . 154 (b ) by 343 days . Treaty ) for International Application No . PCT /US2012 /071432 ,
dated May 21 , 2015 from the International Bureau of WIPO .
(21) Appl. No.: 14 /369,470 International Preliminary Report on Patentability for International
Application No . PCT/US2012 / 071432 , dated May 12 , 2015 from
( 22 ) PCT Filed : Dec. 21 , 2012 the International Bureau of WIPO .
Written Opinion of the International Searching Authonty for Inter
( 86 ) PCT No.: PCT /US2012 /071432 national Application No . PCT/US12/71432 , dated Mar. 5 , 2013
from the International Searching Authority .
$ 371 (c )( 1), Christopher W . Macosco , Rheology : Principles , Measurements, and
( 2 ) Date: Jun . 27, 2014 Applications 141 ( 1994 ), VCH Publishers , Inc . USA .
(87 ) PCT Pub . No.: WO2013/ 101767 * cited by examiner
† cited by third party
PCT Pub . Date : Jul. 4 , 2013
Primary Examiner — Roberto Rabago
(65 ) Prior Publication Data (74 ) Attorney, Agent, or Firm — Finnegan , Henderson ,
US 2015/0025195 A1 Jan . 22 , 2015 Farabow , Garrett & Dunner, LLP
Related U .S . Application Data (57) ABSTRACT
(60 ) Provisional application No.61/631, 209 , filed on Dec . The present disclosure is related to bimodal high -density
29 , 2011. polyethylene polymer compositions with increased high
melt strength and good processability comprising a base
(51) Int . Cl. resin which has a density of about 945 kg/m3 to about 955
C08L 23 / 06 ( 2006 .01) kg/m ", and comprises an ethylene polymer ( A ) having a
CO8L 23 /08 ( 2006 .01) density of at least about 968 kg/ m , in an amount ranging
C08J 3 / 00 ( 2006 .01) from 45 % to 55 % by weight and an ethylene polymer (B )
(52 ) U . S . CI. having a density lower than the density of polymer ( A )
CPC . C08L 23 / 06 ( 2013. 01 ) ; C08J 3/2005 wherein said composition has a complex viscosity at a shear
(2013. 01 ); C08L 23 / 0815 (2013 .01); C08 ) rate of 0 .01 rad /s ranging from about 200 to about 450 kPa:s
2323 /06 ( 2013.01) ; C08J 2323 /08 ( 2013.01) ; and a complex viscosity at a shear rate of 100 rad/s ranging
CO8L 2203/ 18 ( 2013 .01) ; CO8L 2205/02 from about 1900 to about 2500 Pa.s . The present disclosure
(2013 .01 ); CO8L 2207 /062 (2013 .01) also relates to methods of making, and using the present
(58) ???
Field .of.....Classification Search compositions, and to articles made from there composition ,
........... CO8L 23 /06 ; CO8L 23 /0815 ; CO8L and preferably to pipes and fittings.
2205/025 ; C08J 3 / 005 ; C08J 3 / 242; C08J
2323/ 06 ; C08J 2323/ 08 ; C08F 8/ 10 23 Claims, No Drawings
 US 9, 873,782 B2
BIMODAL HIGH -DENSITY POLYETHYLENE PE100 resins respectively. Another requirement for such
RESINS AND COMPOSITIONS WITH pipes is to have very good long term strength as represented
IMPROVED PROPERTIES AND METHODS by the Hydrostatic Design Basis (HDB ). Extrapolation
OF MAKING AND USING THE SAME according to ASTM D2837 shows that they have a 23°
5 C ./100,000 hour intercept of at least 1530 psi. Such resins
CROSS REFERENCE TO RELATED would have an HDB rating of 1600 psi and are known as
APPLICATIONS PE3608 or PE4710 resins depending on other short term
material characteristics such as density and stress crack
This application is a national phase filing of PCT/ resistance . In one embodiment, the present disclosure is
US2012 /071432, filed Dec . 21, 2012, which claims priority 10 directed to pipes manufactured with the polyethylene com
to U . S . Provisional Patent Application No. 61/631, 209, filed positions and resins of the present disclosure . In one
Dec . 29 , 2011 , the content of both incorporated herein by embodiment, the pipes made with the compositions and
reference in their entirety . resins of the present disclosure meet PE 100 specifications.
The present disclosure relates to polyethylene resins, In one embodiment, pipes made with the composition and
more particularly those suitable for use as pipes, pipe 15 resins of the present disclosure meet PE 4710 specifications.
attachments or fittings, and processes for producing such These are polyethylene resins which when used for the
resins . The present disclosure also relates to the use of formation of pipes of specific dimensions, survive a long
polyethylene compounds comprising such resins for the term pressure test at different temperatures for a period of
manufacture of pipes or pipe fittings, and to such fittings 10 ,000 hours . The density of the current basic powder used
themselves. 20 in the production of a PP or PE4710 compound ranges from
For many high density polyethylene (HDPE ) applications , about 0 . 945 g /cm to about 0 . 955 g /cm " , preferably from
polyethylene with enhanced toughness, strength and envi - about 0. 947 to 0. 951 g/cm ", and preferably is about 949
ronmental stress cracking resistance (ESCR ) is desirable . In g /cm ", In certain embodiment, the polyethylene resins con
the context of manufacturing of large diameter thick wall tain conventional amounts of black pigments and exhibit
pipe , melt strength of the polymer is also desirable . 25 densities ranging from about 0 .958 to about 0 . 961 g / cm " .
Increased melt strength helps prevent having the polymer In one embodiment, the present disclosure is also directed
material flow downward due to the effects of gravity . Mate - to polymer compositions with good resistance to sagging . In
rials that sag produce pipe with thicker pipe walls on the one embodiment, the compositions and resins of the present
bottom of the pipe and thinner wall distribution on top of the disclosure could be used for applications where melt
pipe. Pipe industry standards set limits of maximum allow - 30 strength of high -density polyethylene is important, including
able variation in wall thickness . Thus, use of polymers with blow molding, extruded sheet, and film applications. In
high sagging characteristics can result in producing pipes another embodiment, this disclosure is also directed to pipes
that are not compliant or unable to meet certain standards, manufactured with the polyethylene composition and resin
An increase of themelt strength of the polymer, and in turn of the present disclosure and having a diameter greater than
a reduction in sagging , can be accomplished by long chain 35 24 inches and a wall thickness greater than 21/4 inches. Large
branching in the polymer. The long branching prevents the diameter thick pipes generally require high -density polyeth
material from sagging as the material exits the pipe extruder, ylene (HDPE ) with high melt strength . High melt strength
before it enters the vacuum cooling tank . polymer can be provided by the long chain branching in the
The present disclosure is also directed to compositions polymer that prevents the material from sagging as the
with good resistance to sagging. The disclosure is also 40 material exits the pipe extruder, before it enters the vacuum
directed to composition suitable to applications in Which cooling tank . High - density polyethylene resins with poor
higher low shear melt strength of the polymer melt would be melt strength sag, begin to flow downward due to the effects
beneficial including blow molding , extruded sheet and film of gravity , producing pipe with non - uniform wall distribu
applications. In one embodiment the compositions of the tions.Materials that sag produce pipe with thicker pipe walls
present disclosure are used for the manufacture of pipes and 45 on the bottom of the pipe and thinner wall distribution on top
fittings. Polyethylene resins are known for the production of of the pipe, Pipe industry standards set limits of maximum
pipes and fittings. Pipe resins require high stiffness (creep allowable variation in wall thickness . Low sag behavior for
rupture strength ), combined with a high resistance against most pipe extrusion applications can be predicted by a
slow crack growth as well as resistance to rapid crack material' s complex viscosity measured at a frequency of
propagation yielding impact toughness. Polyethylene pipes 50 0 .01 rad/s at a temperature of 190° C . (n * 0.01 ). Examples of
are widely used as they are lightweight and can be easily pipes with low sag behaviour, but poor mechanical proper
assembled by fusion welding . Polyethylene pipes also have ties have been discussed in the art wo 08006487 ,
a good flexibility and impact resistance , and are corrosion EP - 1137707 and EP - B - 1655333 . The compositions of the
free . However unless they are reinforced , they are limited in present disclosure exhibit excellentmechanical properties
their hydrostatic resistance by the inherent low yield 55 such as stress crack resistance , creep resistance and resis
strength of polyethylene . It is generally accepted that the tance to rapid crack propagation .
higher the density of the polyethylene , the higher will be the In another embodiment, the present disclosure is related
long term hydrostatic strength . ISO 9080 , ISO 12162 , to pipe having very high environmental stress crack resis
ASTM D883 and ASTM D3350 describe the classifications tance ( PE100 -RC ), Pipe with these characteristics is suitable
of pipes according to the PE100 and PE4710 specifications. 60 for pipe laying techniques such as sandless installations, or
One requirement for such pipes is to have very good long when the pipe is in contactwith aggressive mediums such as
term strength as measured by the “Minimum Required detergents . For example , the German PAS1075 (Public
Strength ” (MRS ) rating. Extrapolation according to ISO Application Scheme for sandless pipe installation ) requires
9080 shows that they have an extrapolated 20° C ./50 years the following properties for pipes to be labelled PE100 -RC
stress at a lower prediction level (97 .5 % confidence level 65 (for Resistant to Cracks): FNCT> 8 760 h at 80° C . under 4
“ LPL ” ) of at least 8 and 10 MPa ; such resins have an MRS MPa in 2 % Arkopal N100 , Point loading test > 8 760 h at 80°
rating of MRS 8 or MRS 10 and are known as PE80 and C . under 4 MPa in 2 % Arkopal N100 , and NPT> 8 760 h at
 US 9, 873,782 B2
80° C . [ 176° F. ], 9 .2 bar, The compositions of the present in an amountranging from about 45 to about 55 % by weight,
disclosure fulfil the requirements for the PE100 -RC classi preferably from about 47 to about 53 % by weight, preferably
fication . Pipes with good mechanical properties are known from about 48 to about 52 % by weight,most preferably from
in the art, for example in WO 08006487 , and EP - 1985660 . about 49 .5 to about 51 .5 % by weight, and an ethylene
In one embodiment of the present disclosure , reticulation 5 polymer (B ) having a density lower than the density of
is used to improve the melt strength of the polymer com - polymer A , wherein said composition has a complex vis
positions while retaining good processability and good cosity at a shear rate of 0 .01 rad /s ranging from about 200
mechanical properties. In one embodiment , reticulation of to about 450 kPa.s , preferably from about 220 to about 450
the polymer with the addition of peroxide is used to achieve kPa.s , most preferably from about 220 to about 420 kPa:s
the properties of the present composition . Methods for 10 and a complex viscosity at a shear rate of 100 rad / s ranging
increasing the melt strength of HDPE compositions by the from about 1900 Pa :s to about 2600 Pa. s, preferably from
use of thermally decomposable initiators such as peroxides about 2000 to about 2500 Pa.s, most preferably from about
have been discussed in the art. U . S . Pat. No . 4 , 390 ,666 , WO 2100 to about 2450 Pa .s .
08 /006487 , WO 9747682 , WO 2011 /090846 , U . S . Pat. No. The melt index Mic of the polyethylene composition is
4 , 390 ,666 , WO 2008 /083276 , WO 2009 /091730 , U .S . Pat- 15 preferably from about 0 . 1 to about 0 .5 g / 10 min , preferably
ent Publication No. 2007 /0048472, WO 2006 /036348, from 0 . 20 to 0 .45 g / 1.0 min , most preferably from 0 .2 -0 .4
EP1969018 , U .S . Patent Publication No . 2008 /0161526 and g / 10 min . For the purposes of the present disclosure , melt
U .S . Publication No. 2011/0174413 . In one aspect, the flow indices HLMI, MI, and MI, aremeasured according to
present disclosure is also directed to processes and methods ISO1133 at a temperature of 1 . 90 ° C . under loads of 21, 6
to manufacture a bimodal high -density polyethylene pipe 20 kg, 5 kg and 2. 16 kg respectively .
resin with improved melt- strength while maintaining proc The shear thinning index SHI is the ratio of the viscosity
essability and retaining the properties characteristic of PE of the polyethylene composition at different shear stresses ,
100 and USPE 4710 materials . in the present disclosure , the shear stresses at 2 . 7 kPa and
Processability of a polymer composition can be charac - 210 kPa are used for calculating the SHI, 71910 which may be
terized by its viscosity at a given shear stress that would be 25 considered as a measure of the broadness of the molecular
experienced during pipe extrusion . This processability can weight distribution . The SHI, 71010 of the composition pref
be predicted by viscosity measurements such as complex erably ranges from about 60 to about 115 , preferably from
viscosity at 100 rad /s (n * 100 ) for pipe extrusion and /or a about 65 to 105 , most preferably from about 75 to 95 .
melt index test such as HLMI. Processability for most pipe The composition preferably has a G '(G " = 3000 ) (Pa ) rang
extrusion applications can be predicted by a materials 30 ing from about 1600 to about 2500 , preferably from about
complex viscosity measured at a frequency of 100 rad /s at a 1650 to about 2400 , most preferably from about 1700 to
temperature of 190° C . The processability can be directly about 2200 .
measured on pipe extrusion equipment by throughput and The composition preferably has a complex viscosity at a
amperage load required to produce a given pipe size. constant shear stress of 747 Pa ( 9 * 747) preferably from about
The complex viscosity at 100 rad /s (n * 100 ) most closely 35 400 kPa :s to about 1300 kPa.s, preferably from 500 to 900
represents the shear rate imparted on the material during kPa:,s, and most preferably from 550 to 900 kPa.s. In one
pipe extrusion . Viscosity is predictive of processability , i.e . embodiment, the composition has a n * 747 viscosity ranging
extrusion energy demand and ultimately throughput, Within from about 650 to about 900 kPa .s.
the context of the present disclosure, the complex viscosity The composition preferably has a zero shear viscosity
at 100 rad /s (n * 100 ) may also be referred to as the process- 40 (n * .) preferably greater than about 500 kPa .s , preferably
ability viscosity , A polymer composition with a lower pro - greater than 650 kPa .s , and most preferably greater than 800
cessability viscosity value would be easier to process, or kPa .s . In one embodiment , the composition has a n * .
require less energy or amperage to achieve the same viscosity ranging from about 800 to about 1 , 200 kPa.s .
throughput (lbs/hour), when compared to a composition The base resin may optionally further comprise a small
with a high processability viscosity value. If a material' s 45 prepolymerization fraction in an amount of 5 % or less based
processability viscosity is too high , or the material is too on total polyethylene . Alternatively or additionally it may
viscous, the energy required to achieve a desired throughput further comprise a fraction of very high molecular weight
rate may be outside of the capability of the extrusion polymer, having a weight average molecular weight higher
equipment. In this case the total throughput for that resin than the weight average molecular weight components ( A ),
would be the limiting factor, and extrusion rates would have 50 ( B ) or the prepolymer, in an amount of 5 wt % or less based
to be decreased until the energy demand of the line is within on total polyethylene .
the equipment' s capability . For pipe extrusion resins, resins It is generally preferred that the ratio of polymer ( A ) to
with good processability are generally expected to have a polymer ( B ) in the base resin is between 45 :55 and 55 :45 ,
complex viscosity at 100 rad / s ranging from about 1, 900 to more preferably between 47 :53 and 53 :47 , and most pref
about 2 ,600 Pa .s . In one embodiment, the processability is 55 erably between 48 : 52 and 52 : 48 , regardless of the presence
measured by a shear thinning index at 2 .7 kPa and 210 kPa or otherwise of any additional polyethylene fractions,
from about 60 to about 115 , a complex viscosity at 100 The form of the molecular weight distribution curve , i.e .
rads/ s ranging from about 1, 900 Pa. s to 2 ,600 Pa. s, and a the appearance of the graph of the polymer weight fraction
high load melt index (HLMI) ranging from about 6 to 11 as function of its molecular weight, of a multimodal poly
g / 10 min . 60 ethylene such as the base resin will show two or more
In a first aspect, the present disclosure provides a bimodal maxima or at least be distinctly broadened in comparison
high -density polyethylene polymer composition comprising with the curves for the individual fractions. For example , if
a base resin which has a density of about 945 kg/m3 to about a polymer is produced in a sequential multistage process
955 kg/mº, preferably 946 kg/m² to 951 kg/m ”, most pref- utilising reactors coupled in series with different conditions
erably 947 kg /mºto 951 kg/ m ", and comprises an ethylene 65 in each reactor, each of the polymer fractions produced in
polymer ( A ) having a density of at least 968 kg/ m " , pref - the different reactors will have its own molecular weight
erably above 970 kg /m ”, most preferably above 971 kg /m3 distribution and weight average molecular weight. The
 US 9 , 873,782 B2
molecular weight distribution curve of such a polymer The melt index of the second polymer is defined as that
comprises the sum of the individual curves of the fractions, measured for the second polymer when made separately
typically yielding a curve for the multimodal polymer hav - under the same polymerization conditions as used to make
ing a substantially single peak or two or more distinct the multimodal base resin . In other words , the second
maxima. A " substantially single peak ” may not follow a 5 polymer is made separately using the same catalyst and
Gaussian distribution , may be broader than a Gaussian under the same polymerization conditions as those
distribution would indicate , or have a flatter peak than a employed in the second reactor of the multimodal polym
Gaussian distribution , Some substantially singular peaks erization , and its melt index is then measured . The density
may have a tail on either side of the peak . In some embodi- of the second polymer is defined as being that calculated
ments it may be possible to mathematically resolve a " sub - 10 from the relationship : density (resin )= wt % (I)* density ( 1) +
stantially single peak ” in a molecular weight distribution wt % ( 2 ) * density (2 ) where ( 1 ) and (2 ) are respectively the
curve into two or more components by various methods. first and second polymers .
It is particularly preferred that ethylene polymer ( A ) is a The comonomer content of the second polymer is defined
homopolymer , and the ethylene polymer (B ) is a copolymer as being that calculated from the relationship : comonomer
of ethylene and a C4- C , alpha -olefin , 15 content (resin ) = wt % ( 1 )* comonomer content( 1) +wt % ( 2 )
As used within this disclosure , the term “ homopolymer” * comonomer content (2 ) where (1 ) and (2 ) are respectively
is understood to denote an ethylene polymer composed the first and second polymers ,
essentially of monomer units derived from ethylene and If the multimodal polymer is made with a “ multiple
substantially devoid of monomer units derived from other catalyst system ” such as a bimetallic catalyst, it is possible
olefins, which corresponds to a comonomer content of less 20 to make both polymers (A ) and (B ) in the same reactor. In
than about 0 . 15 mol % . The term “ copolymer of ethylene such a case it is not possible to measure directly the
and a C4 - C , alpha- olefin ” is understood to denote a copo - properties of either polymer ( A ) or polymer (B ), Therefore
lymer comprising monomer units derived from ethylene and in this case the properties of both polymers ( A ) and (B ) are
monomer units derived from a C4- C , alpha - olefin and defined as being those obtained when the respective poly
optionally, from at least one other .alpha .- olefin . The C4- C , 25 mers are prepared separately using the individual catalysts
alpha -olefin can he selected from olefinically unsaturated of the “ multiple catalyst system ” , and under the same
monomers comprising from 4 to 8 carbon atoms, such as, for polymerization conditions as those employed formaking the
example, 1 -butene, 1 -pentene , 1 -hexene , 3 -methyl-1 - multimodal polymer.
butene , 3 - and 4 -methyl- 1 -pentenes and 1 -octene. Preferred In one embodiment, the multimodal composition of the
alpha -olefins are 1 -butene, 1-hexene and 1 - octene and more 30 present disclosure comprises a base resin having a density
particularly 1-hexene . More preferred comonomers are ranging from about 947 to about 951 kg/m°, and comprising
Co- Cg alpha -olefin , the most preferred comonomer is 1-hex - an ethylene polymer (A ) having a density of at least 971
ene . kg/ m in an amount ranging from about 48 to about 52 wt % ,
The other alpha - olefin which may also be present addi an ethylene polymer (B ) having a density of about 920 to
tional to the C2- C , alpha - olefin is preferably selected from 35 about 930 kg/m3 in an amount ranging from about 52 to
olefinically unsaturated monomers comprising from 3 to 8 about 48 wt % , and said composition having a comonomer
carbon atoms, such as, for example , propylene , 1-butene , content of ranging from about 0 .30 to about 0 .65 mol % a
1-pentene, 3 -methyl- 1 -butene, 3 - and 4 -methyl- 1 -pentenes, G '(G " = 3000 ) (Pa ) between 1700 and 2200 Pa., a complex
1 -hexene and 1 -octene . viscosity at a shear rate of 100 rad / sec ranging from about
The content in the composition of monomer units derived 40 2100 to about 2450 Pa.s, a complex viscosity at a shear rate
from C . - C . alpha - olefin , hereinafter called cornonomer con - of 0 .01 rad / s ranging from about 220 to about 420 kPa .s .
tent is preferably from about 0.3 to 0.65 mol % , preferably In other embodiments , the polymer compositions may
from about 0 . 4 to 0 .65 mol % , and most preferably from comprise additional components without departing from the
about 0 .4 to 0 .6 mol % . The content in copolymer (B ) of scope of the present disclosure, in particular, the composi
monomer units derived from C4 - C , alpha - olefin is generally 45 tion may contain conventional additives in an amount of up
at least 0 .6 mol % , in particular at least 0 . 8 mol % , The to about 10 wt % , preferably up to about 5 wt % and more
comonomer content of copolymer (B ) is usually atmost 1 .5 preferably up to about 3 wt % based on the total weight of
mol % , preferably at most 1. 1 mol % . the compositionº Such additives include stabilizers ( antioxi
In one embodiment of the present disclosure, polymer ( A ) dizing agents and /or anti-UV agents ), antistatic agents and
has an MI, ranging from about 200 to 600. In one embodi- 50 processing aids, as well as pigments . The composition may
ment of the present disclosure polymer ( A ) has an MI, also contain up to 10 wt % of another polyolefin , preferably
ranging from about 300 to 500 g / 10 min . In one embodi- another polyethylene.
ment, the density of polymer ( A ) preferably ranges from As used in the present disclosure , " multiple catalyst
about 968 kg/m3 to 975 kg/m°, The density of polymer (A ) system ” refers to a composition, mixture or system includ
more preferably ranges from about 970 kg/mºto 974 kg /m ", 55 ing at least two different catalyst compounds , each having
and from 971 to 974 kg/m3. The density of copolymer ( B ) the same or a different metal group, including a " dual
preferably ranges from about 915 kg/m3 to 935 kg/m ", and catalyst,” e. g., a bimetallic catalyst. Use of a multiple
from about 920 kg /m3 to about 930 kg/m². catalyst system enables the multimodal product to be made
If polymers ( A ) and (B ) are made separately and then in a single reactor. Each different catalyst compound of the
blended , it is possible to measure directly the melt index , 60 multiple catalyst system may reside on a single support
density and comonomer content of both polymers . However, particle , in which case a dual ( bimetallic ) catalyst is con
if themultimodal polymer is made in a multistage process in sidered to be a supported catalystº However, the term
which one polymer is made prior to the other and then the bimetallic catalyst also broadly includes a system ormixture
second polymer is made in the presence of the first polymer, in which one of the catalysts resides on . one collection of
the melt index , density and comonomer content of the 65 support particles , and another catalyst resides on another
second polymer cannot be measured , and instead for the collection of support particles . Preferably, in that latter
purposes of this disclosure they are defined as follows: instance , the two supported catalysts are introduced to a
 US 9, 873,782 B2
single reactor, either simultaneously or sequentially, and embodiments according to the present disclosure , the step of
polymerization is conducted in the presence of the bimetallic polymerising ethylene preferably forms a multimodal poly
catalyst system , i. e ., the two collections of supported cata - ethylene.
lysts . Alternatively, the multiple catalyst system includes a The catalyst employed in the polymerization process to
mixture of unsupported catalysts in slurry or solution form . 5 produce the polyethylene base resins used in the composi
In one embodiment according to the present disclosure , tions of the disclosure may be any catalyst(s ) suitable for
the multimodal polyethylene base resin is preferably bimodal preparing such
preparing polyethylenes. If the polyethylene is
suchpreferred
polyethylenes
, it is
obtained by a multistage ethylene polymerization , typically the high and low molecular that the same catalyst produces both
using a series of reactors. A multistage process is a polym 10 the catalyst may be a Ziegler weight fractions. For example ,
erization process in which a polymer comprising two or catalyst. Preferably the catalyst is a Ziegleror-Natta
-Natta catalyst a metallocene
catalyst.
more fractions is produced by producing at least two poly In the case of a Ziegler -Natta catalyst , the catalyst used
mer fraction (s ) in separate reaction stages, usually with comprises at least one transition metal. Transition metal.
different reaction conditions in each stage , in the presence of means a metal of groups 4 , 5 or 6 of the Periodic Table of
the reaction product of the previous stage . The polymeriza - 15 elements (CRC Handbook of Chemistry and Physics . 75th
tion reactions used in each stage may involve conventional edition , 1994 - 95 ), The transition metal is preferably titanium
ethylene homopolymerization or copolymerization reac and /or zirconium . A catalyst comprising not only the tran
tions , e .g . gas-phase , slurry phase , liquid phase polymeriza sition metalbut also magnesium is preferably utilized . Good
tions , using conventional reactors , e . g . loop reactors , gas results have been obtained with catalysts comprising: from
phase reactors, batch reactors etc . 20 5 to 30 % , preferably from 6 to 22 % , most preferably 8 to
It is preferred that the polymer (A ) is produced in the first 18 % by weight of transition metal, from 0 .5 to 20 % ,
reactor, and that polymer ( B ) is produced in a subsequent preferably from 2 to 18 % , most preferably 4 to 15 % by
reactor. However this order may be reversed . If the base weight ofmagnesium , from 20 to 70 % , preferably from 30
resin includes a prepolymer, this is made in a reactor to 65 % , most preferably 40 to 60 % by weight of halogen ,
preceding the first reactor. It is preferred that all reactors are 25 such as chlorine, from 0 .1 to 10 % , preferably from 0 .2 to
slurry reactors , in particular slurry loop reactors. In one 8 % ,most preferably 0 .5 to 5 % by weight of aluminium ; the
embodiment, the preferred multistage polymerization pro - balance generally consisting of elements arising from prod
cess includes in a first reactor, ethylene is polymerized in ucts used for their manufacture, such as carbon , hydrogen
slurry in a first mixture comprising a diluent, hydrogen , a and oxygen . These catalysts are preferably obtained by
catalyst based on a transition metal and a cocatalyst, so as to 30 coprecipitation of at least one transition metal composition
form from 30 to 70 % by weight with respect to the total and a magnesium composition by means of a halogenated
weight of the composition of an ethylene homopolymer ( A ); organoaluminium composition , Such catalysts have been
said first mixture is withdrawn from said reactor and is described in U . S . Pat. Nos. 3, 901, 863; 4 ,292 ,200 and 4 ,617 ,
subjected to a reduction in pressure, so as to degas at least 360 . The catalyst is preferably introduced only into the first
a portion of the hydrogen to form an at least partially 35 polymerization reactor , i.e . there is no introduction of fresh
degassed mixture , and said at least partially degassed mix - catalyst into the further polymerization reactor. The amount
ture, together with ethylene. and a C4- C , alpha-olefin and , of catalyst introduced into the first reactor is generally
optionally , at least one other alpha . - olefin , are introduced adjusted to obtain an amount of at least 0 .5 mg of transition
into a subsequent reactor and the slurry polymerization . is metal per litre of diluent. The amount of catalyst usually
carried out therein in order to form from 30 to 70 % by 40 does not exceed 100 mg of transition metal per litre of
weight, with respect to the totalweight of the composition , diluent .
of a copolymer of ethylene and of C4-Cg alpha -olefin . In one embodiment, a preferred catalysts contain 8 to 18 %
In one embodiment, a low -molecular weight (LMW ) by weight of transition metal, 4 to 15 % by weight of
ethylene polymer component (A ) is made in a first reactor magnesium , 40 to 60 % by weight of chlorine and 0 .5 to 5 %
and a high -molecular weight (BMW ) ethylene polymer 45 by weight of aluminium , and have a residual organic radical
component ( B ) is added in a second reactor, Within the content in the precipitated catalyst of less than 35 wt % .
context of this disclosure the terms “ LMW ethylene polymer These catalysts are also obtained by coprecipitation of at
component ( A )” , “ ethylene polymer component ( A )” or least one transition metal compound and a magnesium
“ LMW ethylene component” may he used interchangeably . compound by means of a halogenated organoaluminium
Similarly, within the context of this disclosure the terms 50 compound , but with a ratio of transition metal to magnesium
“ HMW ethylene polymer component ( B )” , “ ethylene poly - of no more than about 1 : 1 . For additional discussion in these
mer component (B )” or “ HMW ethylene component" may catalyst see EP - B - 2021385 which is incorporated herein in
also be used interchangeably. The mass ratio of LMW its entirety.
ethylene polymer component (A ) to the final bimodal A preferred catalytic system for use in the process of the
FLINT polymer is in an amount ranging from 45 % to 55 % 55 present disclosure comprises a catalytic solid comprising
by weight, preferably from 47 to 53 % by weight, preferably magnesium , at least one transition metal selected from the
from 48 to 52 % by weight, and most preferably from 49.5 group consisting of titanium and zirconium and halogen ,
to 51. 5 % by weight. In one embodiment, the polymerization prepared by successively reacting, in a first step (i) at least
occurs in both reactors in the presence of hydrogen , and the one magnesium compound (M ) chosen from oxygen -con
ratio of molar hydrogen concentration in the first reactor to 60 taining organic magnesium compounds with at least one
molar hydrogen concentration in the second reactor is from compound ( T ) selected from the group consisting of oxygen
250 : 1 to 350 : 1 . containing organic tetravalent titanium and zirconium com
The disclosure also provides a process for obtaining a pounds, until a liquid complex is obtained ; treating, in a
pipe or a pipe fitting, comprising the steps of polymerising second step , the complex obtained in the first step with a
ethylene and optionally comonomer, compounding the poly - 65 halogen -containing aluminic compound of formula
ethylene composition , and then extruding or injection ALRnX3- n , in which Ris a hydrocarbon radical comprising
moulding the composition to form an article. In most up to 20 carbon atoms, X is a halogen and n is less than 3 ,
 US 9, 873,782 B2
10
and an organometallic compound of a metal chosen from polymer and additive feed determines how well the polymer/
lithium , magnesium , zinc , aluminium or tin . additive/decomposable thermal initiators mixture is dis
The preparation of the solid catalytic complex comprises persed . The temperature and residence time in the mixing
the step (ii), the main function of which is to reduce the and extruder cause the decomposable thermal initiators to
valency of the transition metal and simultaneously addition - 5 react with the base polymer .
ally halogenate, if necessary , the magnesium compound In one embodiments , cross - linking of the polymer is done
and / or the transition metal compound : thus most of the using decomposable thermal initiators. The cross - linking of
alkoxy groups still present in the magnesium compound the polymer is controlled by addition of the initiator in
and/ or in the transition metal compound are substituted . by
halogens, such that the liquid complex obtained after step ( i) 10 powder or liquid form in the pre -mix of additives fed in the
extruder, simultaneously with polyethylene powder . The
is transformed in a catalytically active solid . The reduction decomposable thermal initiator may be added as a neat
and possible further halogenation are performed simultane compound or may alternatively be dispersed in another
ously using the halogen -containing aluminic compound polymer as a masterbatch , typically polyethylene or poly
Which thus acts as a reductive halogenating agent, The
treatment using the halogen - containing aluminic compound 15 propylene . The type of initiator is selected according to its
in step ( ii ) of the preparation of the catalytic solid may be half time life curve versus temperature
carried out by any suitable known means, and preferably by Decomposable thermal initiators are known in the art,
gradually adding the halogen -containing organoaluminium such as azobisisobutyronitrile (AIBN ), peroxy compound
compound to the liquid complex obtained in step (i). The such as diacyl peroxides, acetyl alkylsulfonyl peroxides,
temperature at which step (ii) is performed should not 20 dialkyl peroxydicarbonates, tert-alkylperoxyesters, 00 - tert
exceed 60° C ., temperatures of no more than 50° C . being alkyl O -alkyl monoperoxycarbonates, di(tert- alkylperoxy )
the most advantageous . ketals, di( tert -alkyl)peroxides, tert- alkyl hydroperoxides ,
The preferred temperature range is 25 -50° C ., with the and ketone peroxides , redox initiators , and the like.
most preferable range being 30 - 50° C . The cocatalyst uti- In one embodiment, preferred peroxy compounds com
lized in the process is preferably an organoaluminium com - 25 prise diacylperoxides such as dibenzoyl peroxide BPO ,
pound . Unhalogenated organoaluminium compounds of for- di( 2 , 4 - dichlorobenzoyl) peroxide , diacetyl peroxide , dilau
mula AIR , in which R represents an alkyl grouping having royl peroxide , didecanoyl peroxide , diisononanoyl peroxide
from 1 to 8 carbon atoms are preferred . In one embodiment, and succinic acid peroxide; peroxy esters such as di-tert
triethylaluminium and triisobutylaluminium are preferred . butyl diperoxyphthalate, tert- butyl perbenzoate , tert-butyl
In one embodiment, the multistage polymerization pro - 30 peracetate , tert-amyl perbenzoate , 2 ,5 - di(benzoylperoxy ) -2 ,
cess described above for producing the composition of the 5 -dimethylliexane, tert-butyl peroxymaleic acid , tert-butyl
disclosure utilizes a Ziegler-Natta catalyst . In such a case the peroxyisobutyrate, tert -butyl peroxy -2 - ethylhexanoate( tert
polymerization temperature is generally from 20 to 130° C ., butyl peroctoate ), tert- amyl peroctoate , 2 ,5 - di (2 - ethyl
preferably at least 60° C ., and generally it does not exceed hexanoylperoxy )- 2 ,5 - dimethyl- hexane, tert-butyl per
115º C . The total pressure at which the process is effected is 35 oxypivalate, tert -amyl peroxypivalate , tert-butyl
in general from 0 .1 MPa to 10 MPa . In the first polymer- peroxyneodecanoate , tert -amyl peroxyneodecanoate ,
ization reactor, the total pressure is preferably at least 2 .5 a -cumyl peroxyneodecanoate ; diperoxyketals, such as ethyl
MPa. Preferably, it does not exceed 5 MPa. In the further 3 ,3 - di(tertobutylperoxy )butyrate, ethyl 3, 3 - di( tert-amyiper
polymerization reactor, the total pressure is preferably at oxy )-butyrate, n -butyl 4 ,4 ,-di( tert-butylperoxy ) valerate 2 ,2
least 1.3 MPa. Preferably, it does not exceed 4 .3 MPa . 40 di(tert-butylperoxy)butane , 1, 1 -di(tert- butylperoxy )
The period of polymerization in the first reactor and in the cyclohexane, 1 , 1 - di(tert-buty (peroxy) - 3 ,3 ,5 -trimethylcyclo
further reactor is in general at least 20 minutes, preferably at hexane , and 1 ,1 - di( tert-amylperoxy )cyclohexane ;
least 30 minutes . The period of polymerization generally dialkylperoxides, such as 2,5 (tert -butylperoxy)-2 ,5 - dim
does not exceed 5 hours , and preferably it does not exceed ethyl- 3 -hexyne , di- tert-butyl peroxide, tert-butyl-acumyl
3 hours . In this process, a slurry comprising the resin of the 45 peroxide , 2 , 5 - di(tert- butylperoxy ) -2 ,5 - dimethylhexane , a - a '
disclosure is collected at the outlet of the further polymer - di( tert-butyl -peroxy ) - 1, 3 - and 1 ,4 - diisopropylbenzene , and
ization reactor. The composition may be separated from the dicumylperoxide ; peroxydicarbonates such as di -n -propyl
suspension by any known means . Usually , the suspension is peroxydicarbonate , diisopropyl peroxycarbonate , dicetyl
subjected to a pressure expansion ( final expansion ) to elimi- peroxydicarbonate , di-sec -butyl peroxydicarbonate , di (2
nate the diluent, the ethylene, the alpha-olefin and any 50 ethylhexyl)peroxy dicarbonate, and di(4 -ter(-butylcyclo
hydrogen from the composition . hexyl)peroxydicarbonate ; and tert- alkylhydro peroxides
In one embodiment, the material. modified by a decom - such as tert-butyl hydroperoxide, tert-amyl hydroperoxide,
posable thermal initiators such as a peroxide according to cumene hydroperoxide, 2 ,5 - dihydroxyperoxy - 2 , 5 - dimethyl
the present disclosure can be used in the production of thick hexane , pinane hydroperoxide , para -menthane hydroperox
wall pipe within those industry standards,while still meeting 55 ide, and diisopropylbenzene hydroperoxide .
or exceeding PE100 and PE4710 standards, and while In some embodiments of the present disclosure peroxy
maintaining good processability . initiators are selected from : 2 ,5 - dimethyl-2 ,5 -di(tert -butylp
In one embodiment , polymer compositions according to eroxy )hexyne -3 ; 2 ,5 - dimethyl- 2 , 5 -di( tert- butylperoxy )
the present disclosure are reticulated , usually in a post- hexane ; di- tert-butyl peroxide ; 1,3 - 1,4 -di-tert-butylperoxy
production compounding step . The polymer composition 60 isopropyl benzene; tert -butylcumylperoxide ;
can be reticulated using a decomposable thermal initiators . dicumylperoxide ; 3 ,3 ,6 ,6 , 9 ,9 -hexamethyl- 1 ,2 ,4 ,5 -tetracy
The bimodal resin flake produced on the reactor or reactors clononane; 4 , 4 - di-tert -butyl peroxy -n - butylvalerate ; 1, 1 - di
acts as the base material to be modified . This material is fed tert-butyl peroxycyclohexane; tert-butyl peroxybenzoate ;
to the extrusion equipment along with the additive package dibenzoyl peroxide; di(2 ,4 -dichlorobenzoyl)peroxide; di(p
and the decomposable thermal initiators. The extrusion 65 chlorobenzoyl) peroxide; 2,2 -di(tert-butylperoxy )butane;
equipmentmelts the HDPE flake and disperses the additives ethyl- 3 , 3 -bis ( tert -butylperoxy ) butyrate . In one embodi
and the decomposable thermal initiators . Consistency of ment, the compositions and resins according to the present
 US 9, 873,782 B2
11 12
disclosure are treated with 2 ,5 -dimethyl-2 ,5 -di(tert-butylp - available , a HDPE flake or pellet could be used as a carrier
eroxy )hexane and bis (tert -butylperoxyisopropyl)benzene. for the peroxide, a neat liquid peroxide could be used , as
In a preferred embodiment of the present disclosure the well as other forms of the desired peroxide. Other organic
polymer is treated . with 2 , 5 -dimethyl- 2 ,5 - di(tert-butylper - peroxides that could be used include dicumyl peroxide,
oxy )hexane, commercially available under the names Trigo- 5 tert -butylcumyl peroxide, 1,3 - 1,4Bis ( tert-butylperoxyiso
nox 101 and Pergaprop Hx 7 .5 PP , adhered to a PP flake propylbenzene, and 2 . 5 Dimethyl 2 .5 Di?tert-butylperoxyl).
nd
surface at a 7 .5 wt % concentration . In some embodiments, hexyne, and others . Such replacement materials, while not
the amount of neat peroxy initiator used in the cross-linking changing the basic disclosure , would result in the possible
process ranges from about 50 ppm to about 150 ppm by need for a re - calculation in target peroxide concentrations
weight, and preferably from about 50 ppm to about 100 ppm 10 and other
by weight, Preferably the amount of peroxide is sufficient to time neededreactive to
extrusion . conditions, such as residence
achieve proper mixing .
ensure that the resulting polyethylene composition has the
desired complex viscosity at low shear rate (n *601). The mayTighter controls and better peroxide addition methods
improve the properties of the compositions according to
amount of peroxy initiator required to obtain the desired
value depends partly on the melt strength of the original 15 the present disclosure . Extrusion temperature and residence
unreticulated polyethylene as well as on the type ofperoxide time allow the peroxide to fully react once added to the base
used and on the compounding conditions, more specifically resin flake. Temperatures must be high enough and the
the melt temperature and extruder residence time as these peroxide must remain in contact with the polymer for long
factors will influence the reticulation efficiency . enough for the long chain branching to occur. The peroxide
The optimal peroxide loading level will vary based on the 20 used can be added as either a solid or a liquid .
material's starting melt strength and the type of organic The extrusion equipment could also be replaced or altered
peroxide used . Materials with low shear viscosities lower to use many different types of commercially available poly
than 200 ,000 Pa.s generally do not to have the melt strength mer extrusion equipment. The extrusion equipment used
capable of producing thick wall pipe with wall distributions must be capable of providing sufficient heating , residence
within industry specifications. In one embodiment, the load 25 time, and shear (work ) being imparted on the polymer.
of peroxide is controlled to obtain material which exhibits If the extrusion temperature is too high , the peroxide
low shear viscosities at 0 .01 rad /s no greater than about could be consumed before being able to be well dispersed in
450 , 000 Pa.s. In one embodiment, the preferred amount of the polymer matrix , especially if it were to come in contact
peroxide used is below 150 by weight. It is possible to with a hot surface before being mixed with the polymer . The
produce thick wall pipe with materials that have low shear 30 peroxide reaction would begin , but not react with the poly
viscosities greater than 450 ,000 Pa:s , but the increased low mer chains. The desired melt strength increase would not be
shear viscosity of the material would not produce additional achieved in the polymer. If this were to occur, reduced long
advantage , the use of additional peroxide may become cost chain branching would occur and the low shear viscosity of
prohibitive, cause end product processing issues ( such as the bulk HDPE material would not be sufficient. Extrusion
decrease in throughput and undesirable surface imperfec - 35 temperatures may impact the reticulation process . In one
tions ), and could cause physical property degradation . embodiment, the reticulation according to the present dis
Examples of possible processing issues associated with use closure is carried at a temperature lower than about 320° C .
of higher levels of peroxide include the presence of excess In one embodiment, the reticulation according to the present
gels in the material, causing rough surfaces and weak spots disclosure is carried at a temperature lower than about 280°
in the pipe that could lead to early pipe failures under 40 C . (550° F .). The minimum residence time at a certain
pressure . temperature depends on the half life of the peroxide at that
The polyethylene powder produced in a polymerization temperature . The half life at a given temperature will vary
process such as that disclosed above is fed to the extrusion
equipment along with the additive package and the peroxide . Compositions made according to some embodiments of
The extrusion equipment melts the powder and disperses 45 the present disclosure can be mixed with the usual process
any additives and the peroxide . The peroxide must be well ing additives for polyolefins, such as stabilizers (anti oxi
dispersed within the polymer melt, at temperatures hot dizing agents and /or anti -UV agents ), antistatic agents and
enough and residence times long enough to fully initiate the processing aids, as well as pigments.
peroxide and allow the consequent radical chain reactions to Pipes made from the compositions according to some
occur to a sufficient extent to produce the desired effect. The 50 embodiments of the disclosure preferably have one or more
peroxide must be well dispersed within the polymer melt , at of the following properties an MRS 10 rating or better as
temperatures hot enough and residence times long enough to defined by standard ISO / TR 9080 or a PE4710 listing per
fully initiate the peroxide and allow the consequent radical ASTM D883 and ASTM D3350 .
chain reactions to occur to a sufficient extent to produce the Unless otherwise specified , all numbers expressing quan
desired effect of increased melt strength and retained proc - 55 tities of ingredients, reaction conditions , and other properties
essability . The additive feeding hardware must be able to or parameters used in the specification and claims are to be
feed a consistent amount of peroxide, to give a consistent understood as being modified in all instances by the term
(homogeneous ) modified product. “ about,” All numerical ranges herein include all numerical
If a peroxide carrier with a particle size more similar to values and ranges of all numerical values within the recited
the other additives that are being added to the HDPE melt 60 range of numerical values . By way of non -limiting illustra
could be used , the additives could all be combined into a tion , concrete examples of certain embodiments of the
larger tote bin , allowing the additive feeder to feed at higher present disclosure are given below .
rates with less variability to produce better control of organic
peroxide addition rates . Also the type of peroxide used and EXAMPLES
the carrier used to transport the peroxide could be changed 65
(liquid , PP flake, HDPE flake ). The organic peroxide and its Testing Methods
carrier could be replaced with functional alternatives. If Melt Index
 US 9 , 873,782 B2
13 14
Melt indexes were determined according to ISO1133 or (with anti-oxidant additives ), compression -molded sample
ASTM D1238 and the results are indicated in g / 10 min , but onto the parallel plates . The plates are then closed with a
both tests will give substantially the same results , For positive normal force registered on the meter to ensure good
polyethylenes a temperature of 190° C . is applied . MI, is contact After about 5 minutes at 190° C ., the plates are
determined under a load of 2 . 16 kg, MI, is determined under 5 lightly compressed and the surplus polymer at the circum
a load of 5 kg and HLMI is determined under a load of 21.6 ference of the plates is trimmed . A further 10 minutes is
kg . allowed for thermal stability and for the normal force to
Density decrease back to zero . That is, all measurements are carried
Density of the polyethylene was measured according to out after the samples have been equilibrated at 190° C . for
ISO 1183 - 1 (Method A ) and the sample plaque was prepared 10 about 15 minutes and are run under frill nitrogen blanketing.
according to ASTM D4703 (Condition C ) where it was Two strain sweep (SS ) experiments are initially carried
cooled under pressure at a cooling rate of 15° C ./min from out at 190° C . to determine the linear viscoelastic strain that
190° C . to 40° C . would generate a torque signal which is greater than 10 % of
Comonomer Content the lower scale of the transducer, over the full frequency
The C4-C , alpha - olefin content is measured by 13C NMR 15 (e. g . 0 .01 to 100 rad /s ) range. The first SS experiment is
according to the method described in J. C . Randall , JMS- carried out with a low applied frequency of 0 . 1 rad / s. This
Rev.Macromol. Chem . Phys. C29 ( 2 & 3 ), p . 201- 317 ( 1989). test is used to determine the sensitivity of the torque at low
The content of units derived from C4-C , alpha -olefin is frequency . The second SS experiment is carried out with a
calculated from the measurements of the integrals of the high applied frequency of 100 rad /s . This is to ensure that the
lines characteristic of that particular C4 - C , alpha -olefin in 20 selected applied strain is well within the linear viscoelastic
comparison with the integral of the line characteristic of the region of the polymer so that the oscillatory rheological
units derived from ethylene (30 ppm ). A polymer composed measurements do not induce structural changes to the poly
essentially of monomer units derived from ethylene and a mer during testing . In addition, a time sweep (TS) experi
single C2- C , alpha- olefin is particularly preferred . ment is carried out with a low applied frequency of 0 .1 rad / s
Environmental Stress Crack Resistance (ESCR ) 25 at the selected strain (as determined by the SS experiments )
Environmental stress crack resistance (ESCR ) is deter- to check the stability of the sample during testing .
mined by Notched Pipe Test (NPT ). The notched pipe test The frequency sweep (FS ) experiment was then carried
was performed according to ISO 13479: 1997 on a pipe of out at 190° C . using the above appropriately selected strain
diameter 110 mm and thickness 1. 0 min (SDR 11 ). The test level between dynamic frequencies range of 10 - 2 to 100
was run at 80° C . at a pressure of 9 . 2 bar. 30 rad /s, under nitrogen . The dynamic rheological data thus
Stress Crack Resistance (PENT) measured were then analysed using the rheometer software
Another method to measure environmental stress crack ( viz ., Rheometrics RHIOS V4 .4 or Orchestrator Software )
resistance is the Pennsylvania Notched Tensile Test (PENT), to determine the melt elastic modulus G '(G " = 3000 ) at a
ASTM D1473 . PENT is the North American accepted reference melt viscousmodulus (G " ) value of G " = 3000 Pa,
standard by which pipe resins are tested to classify their 35 If necessary , the values were obtained by interpolation
ESCR performance . A molded plaque is given a specified between the available data points using the Rheometrics
depth notch with a razor and tested at 80° C . under 2 .4 MPa software .
stress to accelerate the stress cracking failure mode of a The term “ Storage modulus” , G '(W ), also known as “ elas
material. The time in which the specimen fails, breaks tic modulus ” , which is a function of the applied oscillating
completely or elongates over a certain length , is used for its 40 frequency, w , is defined as the stress in phase with the strain
ESCR classification, A PE4710 by definition must not fail in a sinusoidal deformation divided by the strain ; while the
before 500 hours . Materials described in this patent would term “ Viscous modulus” , G " ( w ), also known as “ loss modu
test over 10 ,000 hours without failure and be considered lus ” , which is also a function of the applied oscillating
high performance materials. frequency , w , is defined as the stress 90 degrees out of phase
Resistance to Rapid Crack Propagation (RCP ) 45 with the strain divided by the strain . Both these moduli, and
Resistance to rapid propagation of cracks (RCP ) is mea - the others linear viscoelastic , dynamic rheological param
sured according to method s4 described in ISO standard eters, are well known within the skill in the art, for example,
13477 . The critical temperature was determined on a pipe of as discussed by G . Marin in “ Oscillatory Rheometry" ,
diameter 110 mm and thickness 10 mm (SDR 11 ) at a Chapter 10 of the book on Rheological Measurement , edited
constant pressure of 5 bar. The critical temperature is defined 50 by A . A . Collyer and D . W . Clegg , Elsevier , 1988 .
as the lowest crack arrest temperature above the highest Melt Rheology at Constant Shear Stress
crack propagation temperature ; the lower the critical tem The Theological properties of a material at a low shear
perature , the better the resistance to rapid crack propagating . rates were measured to better understand the material as it
Creep Resistance sags under gravitation forces . A constant stress test was used
Creep resistance is measured according to ISO 1167 on a 55 to determine the complex viscosity n * at low shear stress .
pipe of diameter 50 mm and thickness 3 mm (SDR17 ) pipes The experiments were conducted using an ARES G2manu
to determine the lifetime prior to failure at a temperature of factured by TA instruments . In this transient experiment, the
20° C . and 80° C . and a stress of between 5 and 13 MPa. sample was placed under a low shear stress where the
Melt Rheology at Constant Shear Rate viscosity was no longer shear stress dependent. In this region
Dynamic rheological measurements to determine the 60 at very low shear stresses , the shear rate is also expected to
complex viscosities n * as a function of shear rate are carried be very low , much lower than the complex viscosity mea
out, according to ASTM D 4440 , on a dynamic rheometer sured at 0 .01 rad /s, and the viscosity in the region is
(e .g ., ARES ), such as a Rheometrics , Ares model 5 rotational expected to be shear rate independent. The compliance is a
rheometer, with 25 mm diameter parallel plates in a dynamic function of shear stress and time and defined as the ratio of
mode under an inert atmosphere. For all experiments , the 65 time dependent strain over a constant stress . The experi
rheometer has been thermally stabilised at 190° C . for at ments were conducted at low shear stress values where the
least 30 minutes before inserting the appropriately stabilized creep compliance becomes independent of shear stress and
 US 9 ,873, 782 B2
16
linear with time allowing the determination of zero shear TABLE 1
viscosity . The inverse slope of the compliance plot can be
Polymerization conditions and properties for base polymer I
defined as thematerial's zero shear viscosity and can be seen -
in Table 1 . The experiments were carried out at 190° C . EXAMPLE I
-
under nitrogen using a 25 mm diameter parallel plate. The 5 Reactor 1
distance between the parallel plates during the experiment
was 1. 7 mm + 1 % . Stress control loop parameters were run C2 (mol % ) 1.75
and calculated prior to the test using a strain amplitude H2/ C2 (mol/mol % ) 42 . 1
determined in the linear viscoelastic region . A total time of T (°C.) 95
6 minutes was used to condition the sample and transducer. 10 Residence time (h ) 2. 17
wt % ( A ) 49
A low shear stress of 747 Pa is then applied to the sample MI2 ( g/10 min )* 400
and maintained for 1800 seconds, After this time the vis Density (kg/m ) 973
Reactor 2
cosity of the sample is measured . The zero shear viscosity is
determined from the time dependent creep compliance . 15
15 C2 (mol % ) 2.61
Preparation of Black Composition C6 /C2 (mol/mol % )
H2/C2 (mol/mol % )
137. 3
0 .19
The manufacture of a base resin I comprising ethylene TC.) 85
polymers was carried out in suspension in isobutane in two Residence time (h ) 0 . 87
loop reactors , connected in series and separated by a device Final composition (base resin )
Which makes it possible continuously to carry out the 20 MI, ( g/10 min )* 0 . 31
reduction in pressure. Isobutane, ethylene , hydrogen , trieth Density (kg/m ?) 948. 5
ylaluminium and the catalyst were continuously introduced Comonomer content (mol % ) 0 .60
into the first loop reactor and the polymerization of ethylene *Measured according to IS01133
was carried out in this mixture in order to form the homopo
lymer ( A ). This mixture, additionally comprising the 25
homopolymer ( A ), was continuously Withdrawn from the TABLE 2
said reactor and was subjected to a reduction in pressure, to Pelletisation condition and properties of pelletised resins
remove at least a portion of the hydrogen . The resulting
mixture , at least partially degassed of hydrogen , was then EXAMPLE
continuously introduced into a second polymerization reac
c1 2 3 4
Pelletisation conditions
tor, at the same time as ethylene , 1-hexene , isobutane and
hydrogen , and the polymerization of the ethylene and of the DHBP 7 .5 % IC5 0 400 700 1000
hexene was carried out therein in order to form the ethylene/ Peroxide amount ( ppm MB ) 0 30 75
1-hexene copolymer
yn (( BD )) :. The
The suspension
suspension compus the 335 Peroxide
comprising de amount (ppm pure )
Carbon black content wt % ) 2 .2
30
2.1
53
2. 2 2 .2
composition comprising ethylene polymers was continu Total specific energy [kWh/t ] 278 278 279 280
ously withdrawn from the second reactor and this suspen Max melt tempera 312 313 314 312
Properties polymer composition (after pelletisation -black compound )
sion was subjected to a final reduction in pressure , so as to
flash the isobutane and the reactants present (ethylene , MI, (g/ 10 min )* * 0 .29 0 .26 0 .25 0 . 24
hexene and hydrogen ) and to recover the composition in the 40 HLMI (g/10 min )* * 8.5 9.2 9. 8 9. 5
HLMI/MI
form of a dry powder, which was subsequently treated in a Density 29 35 38 40
(kg/m ) 9599 . 959 .2 959 .8 959.0
purge column in order to remove most of the process G '(G ” = 3000) (Pa) 1,276 1,664 1, 927 2 ,096
components trapped in the polymer particles . Catalysts were n * 0.01 (Pa · s ) 185 ,778 215 ,823 257 ,745 299 ,653
used as described in EP - B - 2021385 . The other polymeriza nSHI* 100 (Pa s ) 2 ,504 2 ,382 2 , 396 2 ,401
2.7 /210 ( - ) 44 61 76 96
tion conditions and copolymer properties are presented in 45 nn ** atat GG ** == 22 ..77 kPa
kPa ((PaPa · s ) 150,519 197,229 255,503 311 ,613
Table 1 . n * 747 (kPa ' s ) 280 446 647 889
Additives were incorporated to the powder particles and NPT 80° C . - 9 .2 bar on 110SDR11 > 8 800 > 8 800 > 8 800 > 8 800
subsequently intensively mixed together prior to feeding the pipes (h )
RCP S4 Critical Temperature on - 17.5 - 27 .5 - 17 . 5
compounding equipment, a conventional twin screw 110SDR11 pipes (° C .)
extruder. The additives included at least one acid neutralizer 50 creep at 20° C ./ 12 .4 MPa (h ) 2 , 269 688 803
like calcium stearate or zinc stearate in an amount between creep at 20° C ./ 12. 1 MPa (h ) 2,632 3,0802 , 139 3,066
500 and 2000 ppm or a mixture of both , and at least one creep creep at 20° C ./ 11 .8 MPa (h ) > 7 ,200 > 7 ,200 > 7 ,200 > 7 , 200
process antioxidant like Irgafos 168 in an amount between at 80° C ./5 .7 MPa (h ) 207 490 1,236 4 ,066
creep at 80° C ./5 .5 MPa (h ) > 7 , 800 > 7 ,800 > 7 ,800 > 7 ,800
500 and 2500 ppm and a at least one thermal antioxidant like
Irganox 1010 in an amount between 500 and 2500 ppm , 55 ** measured according to IS01133
Small quantities of processing aid , such as SOLEF 11010 / Preparation of Natural Composition
1001, may also be added . The additives also include Carbon
Black in an amount of 2 .0 - 24 wt % . A thermal decompo described The manufacture of a base resin II was carried out as
sition agent, 2 .5 -dimethyl- 2 ,5 -di(tert -butylperoxy )hexanc for base resin I above . Polymerization conditions
(DI-IBP ) is optionally incorporated in the feed via a 7.5 wt 60 and copolymer properties are presented in Table 3 .
% master batch in polypropylene . 2.5 - Dimethyl-2 ,5 -di(tert-butylperoxy )hexane (DLBP )
This mixture of flake / additives /peroxide enters themixing was incorporated to the powder particles and subsequently
section of the extruder where the material is heated , melted , intensively mixed together prior in a Farrel FCM mixer. The
and mixed together. The time the material spends in the balance of the additive formulation ( Primary antioxidant,
mixing and extrusion sections is considered the reaction 's 65 etc.) is added via a separate feeder at the same location . This
residence time. The other pelletization conditions and prop - mixture of flake /additives /peroxide enters the mixer where
erties of the pelletized resin are specified in Table 2 . the material is heated , melted , and mixed together . A poly
 US 9 ,873, 782 B2
18
mer ribbon then leaves the mixer through the orifice and is TABLE 4 -continued
fed to the extruder. Thematerial is conveyed to the diewhere Example
it is then pelletized . The processing time in the mixer and the
extruder is defined as the residence time. Pipe Size 28 " 24 " 30 " 48 "
Table 4 presents data for reticulated samples and non - 5 Wall Thickness Limitation DR 11
21/4 "
DR 5
4. 5 "
DRO
3 .33"
DR 17
2 .82 "
reticulated samples. These predictive theological tools show 4" 3 .5 "
no statistically significant difference in processing param (inches) or higher or higher
eters while a significant shift in low shear viscosity is
present. To confirm the predictive measurement for proc 10 **Measured according to ASTM D1238
essability and to show that no loss in processability was 10 constraints . on extruder capability, extruder size, pipe size and downstream cooling
* Dependent
experienced comparisons of pipe extrusion measurements of Other embodiments will he apparent to those skilled in the
processability are shown in the Table 4 . Furthermore , the art from consideration of the specification and practice of the
predictive measurement for melt strength was examined anda present disclosure . It is intended that the specification and
confirmed by the pipe extrusion data offered for reticulated 15 examples he considered as exemplary only, with a true scope
and non -reticulated samples . The wall thickness improve - and spirit of the invention being indicated by the following
ments and similar processability show that a peroxide modi
claims.
fied resin will exhibit improved melt strength with no loss of
processability as expected from predictive rheological What is claimed is:
results . 20 1. A bimodal high -density polyethylene pipe extrusion
resin comprising an ethylene polymer ( A ) having a density
TABLE 3 of at least about 968 kg/m in an amount ranging from about
Polymerization conditions and properties for base polymer II 45 % to about 55 % by weight, and an ethylene polymer (B )
having a density lower than the density of ethylene polymer
EXAMPLE
EXAMPLE II 25 ( A ),
wherein said resin has a density of about 945 kg/m2 to
Reactor 1
about 955 kg/mº, a zero shear viscosity (n * .) greater
C2 (mol % ) 3. 3 than about 800 kPas , a complex viscosity at a shear rate
H2/ C2 (mol/mol % ) 47 of 0 .01 rad /s ranging from about 200 to about 450
T (°C .) 96 30 kPa.s, a complex viscosity at a shear rate of 100 rad /s
wt % ( A ) 49 .5
MI2 (g /10 min )* 400 ranging from about 1900 to about 2600 Pa .s , a melt
Density (kg/m ") 972 index MI, ranging from about 0 . 1 to about 0 .5 g / 10
Reactor 2 min , an HLMI ranging from 7 to 11 g / 10 min and a
C2 (mol % ) 3 .0
PENT failure time greater than 7900 hours .
C6 /C2 (mol/mol % ) 130 35 2 . The pipe extrusion resin according to claim 1 , wherein
H2/C2 (mol/mol % ) 0 . 17 the resin has a viscosity at a constant shear stress of 747 Pa
TC.)
Final composition (base resin )
85 (n * 747) ranging from about 400 kPa .s to about 1300 kPa .s .
3 . The pipe extrusion resin according to claim 1 , wherein
MI, (g /10 min )* 0 . 30 the resin has a G '(G " = 3000 ) ( Pa ) ranging from about 1600
Density (kg/m ^) 949 40 to about 2500 .
*Measured according to ASTM D1238
4 . The pipe extrusion resin according to claim 1, wherein
the resin has a comonomer content ranging from about 0 . 3
to about 0 .65 mol % .
TABLE 4 5 . The pipe extrusion resin according to claim 1, further
45 comprising a decomposable thermal initiator in an amount
Example C5 6 7 8 ranging from about 50 ppm to about 150 ppm .
Pelletization conditions
6 . A process for producing a bimodal high -density poly
ethylene pipe extrusion resin comprising :
Peroxide amount (ppm pure ) 0 75 92 130 preparing a bimodal high -density polyethylene base resin
Properties polymer composition (after pelletization -natural compound) 50 comprising an ethylene polymer ( A ) having a density
MI, (g / 10 min )* * 0 . 26 0 . 26 0 .19 0 .22
of at least about 968 kg/ m in an amount ranging from
HLMI (g/10 min )* * 7. 3 8 .4 7 .0 7 .2 about 45 % to about 55 % by weight, and an ethylene
HLMI/MIG 27 .6 32 . 6 36 .6 32. 9 polymer (B ) having a density lower than the density of
Density (kg/m3) 948. 4 949 . 0 948 .9 949 . 7 ethylene polymer (A ), wherein the composition has a
G '(G ” = 3000 ) (Pa ) 1,248 1, 851 1,985 55
55 density of about 945 kg/m² to about 951 kg /mº;
G '(G ” = 5000 ) (Pa ) 2 , 370 3 ,378 3 ,834 feeding the bimodal high -density polyethylene base resin
n *0.01 (Pa . s) 187,073 261, 190 364, 960 428 ,436
n * 100 (Pa · s ) 2304 2272 2,403 2 ,330 into an extrusion device ;
Zero Shear Viscosity (no) 426 ,112 876 ,962 1,295 ,824 3,028 ,376 mixing a decomposable thermal initiator in an amount
(Pa · s ) ranging from about 50 ppm to about 150 ppm over the
SHI 2 .7 /210 3991 115 60
60 weight of the resin into the extrusion device ; and
n * at G * = 2.7 kPa (kPa s)
*

168.3 257.8 399.9 wherein the resulting bimodal high -density polyethylene
n * 747 (kPa · s )
*

1,296
PENT Failure Time (h )
T

> 10 ,000 > 7 ,900 > 10 ,000 pipe extrusion resin exhibits a zero shear viscosity
Pipe Extrusion Data (n * .) greater than about 800 kPas, a complex viscosity
Typical Throughput Rates 1,885 1,500 1,750 2,351 at a shear rate of 0 .01 rad/s ranging from about 200 to
( lb /hr ) * * 65 about 450 kPa . s, a complex viscosity at a shear rate of
Extruder Load ( % ) 70 83 77 73 100 rad /s ranging from about 1900 to about 2600 Pa:s ,
a melt index MI, ranging from about 0 . 1 to about 0 .5
 US 9 ,873,782 B2
20
g /10 min , an HLMI ranging from 7 to 11 g / 10 min and 13 . The process according to claim 9 , wherein the decom
a PENT failure time greater than 7900 hours . posable thermal initiator is selected from the group consist
7. The process according to claim 6 , wherein the base ing of 2,5 Dimethyl 2,5 Di?tert-butylperoxyl)hexane ,
resin comprises ethylene polymer ( A ) in an amount ranging dicumyl peroxide , tert-butylcumyl peroxide, 1,3 - 1,4 Bis
from about 47 % to about 53 % by weight. 5 ( tert- butylperoxyisopropyl) benzene, di- tert-butyl peroxide
8 . The process according to claim 6 , wherein the decom and 2 ,5 Dimethyl 2, 5 Di(tertbutylperoxyl ) hexyne -3 .
posable thermal initiator is selected from the group consist 14 . The process according to claim 13 , wherein the
ing of 2 ,5 Dimethyl 2 ,5 Di?tert-butylperoxyl)hexane, amount of decomposable thermal initiator ranges from about
dicumyl peroxide, tert-butylcumyl peroxide, 1, 3 - 1 ,4 Bis(ter
butylperoxyisopropyl) benzene, di- tert-butyl peroxide and 10 50 15ppm . The
to about 150 ppm .
process according to claim 9 ,wherein the bimodal
2 ,5 Dimethyl 2 ,5 Di?tert-butylperoxyl) hexyne -3 . high - density polyethylene pipe extrusion resin exhibits a
9 . A process for producing a bimodal high -density poly melt index MI , ranging from about 0 .1 to about 0 .5 g/ 10
ethylene pipe extrusion resin comprising: min .
preparing an ethylene polymer component ( A ) having a
density of about 968 kgmto
/ 975 kg/m3 and a MI, 15 16 . The bimodal high - density polyethylene pipe extrusion
ranging from about 200 to 600 g/10 min in a first resin according to claim 1, wherein the bimodal high -density
reactor ; polyethylene pipe extrusion resin exhibits a shear thinning
transferring the ethylene polymer ( A ) to a second reactor index SHI, 71910 ranging from about 60 to about 115 .
and combining ethylene polymer (A ) with an ethylene 17. The bimodalhigh -density polyethylene pipe extrusion
polymer ( B ) having a density lower than the density of 20 resin according to claim 1, wherein the bimodal high -density
ethylene polymer ( A ) to form a bimodal high -density polyethylene pipe extrusion resin exhibits a zero shear
polyethylene base resin with about 45 % to about 55 % viscosity ( n * . ) ranging from about 800 kPas to about 1200
by weight of ethylene polymer ( A ), wherein the first kPas .
and second reactors are fed with hydrogen and the ratio 18 . The process according to claim 6 , wherein the pipe
of the molar hydrogen concentration in the first reactor 25 extrusion resin exhibits a zero shear viscosity (n * ) ranging
to the molar hydrogen concentration of the second from about 800 kPas to about 1200 kPas .
reactor is from 250 : 1 to 350 : 1 ;
feeding the bimodal high -density polyethylene base resin resin19 .made
The bimodal high - density polyethylene pipe extrusion
according to the process of claim 6 , wherein the
and a decomposable thermal initiator to an extrusion bimodal high -density polyethylene pipe extrusion resin
device ; and exhibits a viscosity at a constant shear stress of 747 Pa
mixing high -density polyethylene base resin and the
decomposable thermal initiator, until homogeneous, to (9 * 747) ranging from about 400 kPa.s to about 1300 kPa.s.
obtain the bimodal high -density polyethylene pipe 20 . The bimodal high -density polyethylene pipe extrusion
extrusion resin ; resin made according to the process of claim 6 , wherein the
wherein the bimodal high - density polyethylene pipe 35 bimodal high -density polyethylene pipe extrusion resin has
extrusion resin has a zero shear viscosity (n * .) greater a G '(G " = 3000 ) (Pa) ranging from about 1600 to about 2500 .
than about 800 kPas, a complex viscosity at a shear rate 21 . The bimodal high -density polyethylene pipe extrusion
of 0 .01 rad / s ranging from about 200 to about 450 resin made according to the process of claim 9 , wherein the
kPa:s , a complex viscosity at a shear rate of 100 rad /s bimodal high -density polyethylene pipe extrusion resin
ranging from about 1900 to about 2600 Pa. s , and an 40 exhibits a viscosity at a constant shear stress of 747 Pa
HLMI ranging from 7 to 11 g /10 min and a PENT (n * 747) ranging from about 400 kPa.s to about 1300 kPa.s.
failure time greater than 7900 hours .
10 . The process according to claim 9 , wherein the mixing resin22 .made The bimodal high -density polyethylene pipe extrusion
according to the process of claim 9 , wherein the
step
C .) .
is carried out at temperatures up to about 30° F . ( 288 bimodal high -density polyethylene pipe extrusion resin has
45 a G '( G " = 3000 ) ( Pa ) ranging from about 1600 to about 2500 .
11 . The process according to claim 9 ,wherein the bimodal
high -density polyethylene pipe extrusion resin has a shear high23-.density The process according to claim 6 , wherein the bimodal
polyethylene pipe extrusion resin has a shear
thinning index SHI2.7/210 from about 60 to about 115.
12 . The process according to claim 9 , wherein ethylene thinning index SHI2.7/210 ranging from about 60 to about
polymer ( B ) is polymerized in the presence of 1 -butene , 50 .
1 -hexene, or 1 -octene . * * * *