# Patent

## Title
Ultrahigh molecular weight polyethylene articles and method of manufacture

## Abstract

An article of manufacture comprises an ultrahigh molecular weight polyethylene (UHMWPE) mixed with a processing oil and a lubricant selected from the group consisting of fatty acid esters, ethoxylated fatty acid esters, glycol esters, PEG esters, glycerol esters, ethoxylated esters, sorbitol esters, ethoxylated sorbitol esters, aromatic ethoxylates, alcohol ethoxylates, mercaptan ethoxylates, modified ethoxylates, amide surfactants, phosphate esters, phosphonate esters, phosphite esters, alkyl sulfates, fatty acid ethers, alkyl ether sulfates, alkylaryl ether sulfates, sulfonates, naphthalene sulfonates, sulfosuccinates, sulfonated esters, sulfonated amides, alkyl ether carboxylates, alkylaryl ether carboxylates, quaternary amines, amino quaternary amines, ethoxylated amines, imidazoline derivatives, betaines, sultaines, aminopropionate, catechol derivatives, saturated fatty acids, unsaturated fatty acids, and combinations thereof. The method for making those articles is also disclosed.

## Background
REFERENCE TO RELATED CASES
This Application is a Divisional Application from application Ser. No. 10/121,278 filed Apr. 12, 2002, now U.S. Pat. No. 7,238,744.


FIELD OF THE INVENTION
The invention is directed to ultrahigh molecular weight polyethylene (UHMWPE) articles and their manufacture.
BACKGROUND OF THE INVENTION
UHMWPE is difficult to process because the resin does not flow when melted. Berins, M. L., ed., Plastics Engineering Handbook of the Society of the Plastic Industry, Chapman & Hall, New York City, N.Y. (1991), p. 52. Consequently, UHMWPE is processed by sintering, compression molding, ram extrusion, or gel processing. Sintering is a process where resins are agglomerated by solid-state diffusion. Heat and pressure are usually essential. Compression molding is a process where resins are shaped between the faces of a mold by heat and pressure. Ram extrusion is a process where resins are shaped by forcing it through a die. The force is provided by a ram. U.S. Pat. Nos. 5,234,652 and 5,399,308 disclose a dry extrusion process for a mixture consisting of resins and lubricant. Gel processing is a process where resins are formed into gels for subsequent processing. The gel is a dilute solution or suspension of resin in a solvent, e.g., an extractable solvent (or oil or plasticizer).
UHMWPE is gel spun into fibers. In gel spinning, the primary mechanism of solidification is the gelling of the polymer solution by cooling to form a gel filament consisting of precipitated polymer and solvent. Solvent removal is accomplished following solidification by washing in a liquid bath. This process is also used to form microporous films. See U.S. Pat. Nos. 4,588,633 and 5,248,461. In U.S. Pat. No. 4,588,633, the gel solution consists of 2-4% by weight of UHMWPE. See Examples 1-12. In U.S. Pat. No. 5,248,461, the gel solution consists of up to 20% by weight of UHMWPE. See Examples 1-20. These membranes are useful as, among other things, separators for electrochemical cells. See U.S. Pat. No. 4,588,633, column 4, lines 30-36 and U.S. Pat. No. 5,248,461, column 4, lines 57-60.
Another variant of gel processing is gel processing with a filler. For example, see U.S. Pat. Nos. 3,351,495, 4,833,172, and 5,948,557. Generally, UHMWPE, a processing oil (or plasticizer), and a filler are mixed in an extruder and subsequently made into microporous sheets. In U.S. Pat. No. 3,351,495, the solution consisted of up to 20% by volume of UHMWPE. See Examples 6, 8, 18, 19, 20, and 21. The microporous membranes formed were used as separators for batteries. See column 1, lines 24-33. In U.S. Pat. Nos. 4,833,172 and 5,948,557, a calcium/zinc stearate lubricant, PETRAC® CZ-81, is added to the solution. See Tables 1 and 2, respectively. The microporous membranes formed were used as labels, diffusion membranes, and separators. See U.S. Pat. No. 5,948,557, column 1, lines 27-41.
There is a need to improve the processability of UHMWPE.
SUMMARY OF THE INVENTION
An article of manufacture comprises an ultrahigh molecular weight polyethylene (UHMWPE) mixed with a processing oil and a lubricant selected from the group consisting of fatty acid esters, ethoxylated fatty acid esters, glycol esters, PEG esters, glycerol esters, ethoxylated esters, sorbitol esters, ethoxylated sorbitol esters, aromatic ethoxylates, alcohol ethoxylates, mercaptan ethoxylates, modified ethoxylates, amide surfactants, phosphate esters, phosphonate esters, phosphite esters, alkyl sulfates, fatty acid ethers, alkyl ether sulfates, alkylaryl ether sulfates, sulfonates, naphthalene sulfonates, sulfosuccinates, sulfonated esters, sulfonated amides, alkyl ether carboxylates, alkylaryl ether carboxylates, quaternary amines, amino quaternary amines, ethoxylated amines, imidazoline derivatives, betaines, sultaines, aminopropionates, catechol derivatives, saturated fatty acids, unsaturated fatty acids, and combinations thereof. The method for making those articles is also disclosed.


DESCRIPTION OF THE INVENTION
An article of manufacture is any shaped article. For example, articles of manufacture may include, but is not limited to, films, fibers, sheets, plates, slabs, bars, rods, billets, and blocks. Preferably, these articles are made by an extrusion process. These articles also may be microporous, for example, microporous sheets and films.
Ultrahigh molecular weight polyethylene (UHMWPE) is a polyethylene polymer having a weight average molecular weight greater than 5×105. The polymer is either a homopolymer of ethylene or a copolymer of ethylene, with at most 10 mol % of one or more alpha-olefins. The polymer may be a blend with UHMWPE comprising at least 50% by weight of the blend and the balance being other polymers, such as, for example, polyolefins and synthetic and natural rubbers. The preferred weight average molecular weight is greater than 2×106. The most preferred UHMWPE has a weight average molecular weight greater than 5×106. UHMWPE resins are commercially available as GUR from Ticona LLC of Summit, N.J., STAMYLAN from DSM of Geleen, Netherland, UTEC from Polyailden of Camacari, Brazil, and HI-ZEX Million, LUBMER, and MIPELON, each from Mitsui Chemical of Tokyo, Japan. GUR 4130 (molecular weight about 4-5 million) and GUR 4170 (molecular weight about 8-9 million) are preferred.
Processing oil (or processing plasticizer) have little solvating effect on the UHMWPE at lower temperatures (e.g. 60° C.), but have a significant solvating effect at elevated temperatures (e.g. 200°). Such oils include paraffinic oils, naphthalenic oils, and aromatic oils, as well as other materials including the phthalate ester plasticizers such as dibutyl phthalate, bis(2-ethylene)phthalate, diisodecyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, and ditridecyl phthalate. Additional oils, plasticizers, and/or solvents are mentioned in U.S. Pat. Nos. 3,351,495; 4,588,633; 4,833,172; 5,248,461; and 5,948,557 are incorporated herein by reference.
The filler includes any particulate filler as is well known in the art. For example, see U.S. Pat. Nos. 3,351,495; 4,833,172; and 5,948,557 each is incorporated herein by reference. Preferably, the filler is a silica. Such fillers are commercially available under the tradename HiSil® from PPG Industries, Inc. of Pittsburgh, Pa., SIPERANT from Degussa AG of Wesseling, Germany, ZEOSIL from Rhodia, Inc. of Cranberry, N.J. or KETJENSIL from Akzo Chemie of Compiegne, France.
Minor amounts of auxiliary components may be added. Such auxiliary components include: carbon black, stabilizers, and antioxidants. The compounds are conventional and known in the art.
Lubricants are compounds that, when added to an UHMWPE mixture, improve the processability of the UHMWPE mixture. Improved processability refers to a reduction in fusion time (the time it takes the polymeric system to melt (or dissolve) into a flowable solution). Improved processability is also seen as a reduction in energy consumption by the motor and as a reduction in mixture temperature when comparing systems with and without the lubricants. The results arising from this phenomenon include, but are not limited to, decreasing energy consumption, decreased thermal and mechanical degradation of the polymer, increased polymer strength, decreased machine wear, and increased polymer throughputs.
Such lubricants are selected from the material classes consisting of: fatty acid esters, ethoxylated fatty acid esters, glycol esters, PEG esters, glycerol esters, ethoxylated esters, sorbitol esters, ethoxylated sorbitol esters, aromatic ethoxylates, alcohol ethoxylates, mercaptan ethoxylates, modified ethoxylates, amide surfactants, phosphate esters, phosphonate esters, phosphite esters, alkyl sulfates, fatty acid ethers, alkyl ether sulfates, alkylaryl ether sulfates, sulfonates, naphthalene sulfonates, sulfosuccinates, sulfonated esters, sulfonated amides, alkyl ether carboxylates, alkylaryl ether carboxylates, quaternary amines, amino quaternary amines, ethoxylated amines, imidazoline derivatives, betaines, sultaines, aminopropionate, catechol derivatives, saturated fatty acids, unsaturated fatty acids, and combinations thereof. Preferably, the lubricants are selected from the material classes consisting of: fatty acid esters, ethoxylated fatty acid esters, PEG esters, ethoxylated esters, sorbitol esters, ethoxylated sorbitol esters, aromatic ethoxylates, alcohol ethoxylates, phosphate esters, phosphonate esters, phosphite esters and combinations thereof. Most preferred are sorbitol esters, ethoxylated sorbitol esters, and aromatic ethoxylates.
Such lubricants are commercially available. An exemplary list is set out in the Table below. Such lubricants specifically exclude the metallic salts of stearic acid (e.g., Zn stearate and Ca stearate) and lubricants containing same.










TABLE










Tradename or
General Class of




Abbreviation
Surfactants
Specific chemical
Company





Rhodasurf ® LA-12
Alcohol Ethoxylates
Mixed linear alcohol ethoxylate
Rhodia HPCII


Rhodasurf ® LA-3
Alcohol Ethoxylates
Mixed linear alcohol ethoxylate
Rhodia HPCII


Rhodapex ® CD-128
Alkyl (and Alkyllaryl) Ether
Ammonium Linear Alcohol Ether
Rhodia HPCII



Sulfate
Sulfate


Rhodapon ® BOS
Alkyl Sulfates
Sodium 2-ethylhexyl Sulfate
Rhodia HPCII


Rhodapon ® UB
Alkyl Sulfates
Sodium Lauryl Sulfate
Rhodia HPCII


Alkamide ® STEDA/B
Amide surfactant
Ethylene Bisstearamide
Rhodia HPCII


Igepal ® CO-210
Aromatic Ethoxylates
Nonylphenol ethoxylates
Rhodia HPCII


Igepal ® CO-630
Aromatic Ethoxylates
Nonylphenol ethoxylates
Rhodia HPCII


Igepal ® RC-630
Aromatic Ethoxylates
Dodecyl Phenol Ethoxylates
Rhodia HPCII


Mirataine ® CBS
Betaines, Sultaines, and
Coco/Oleamidopropyl Betaine
Rhodia HPCII



Aminopropionates


Mirataine ® COB
Betaines, Sultaines, and
Cocamidopropyl Hydroxy Sultaine
Rhodia HPCII



Aminopropionates


Miranate ® LEC-80
Ether Carboxylate
Sodium Laureth 13 Carboxylate
Rhodia HPCII


Rhodameen ® PN-430
Ethoxylated Fatty Amines
Ethoxylated (5 moles) tallow amine
Rhodia HPCII


Rhodameen ® T-50
Ethoxylated Fatty Amines
Ethoxylated (50 moles) tallow
Rhodia HPCII




amine


Calcium Stearate
Fatty acids, saturated
Calcium stearate


Linseed Oil
Fatty acids, unsaturated
Linoleic and linolenic acids
Hardware Store


Tung Oil
Fatty acids, unsaturated
Eleostearic acid
Hardware Store


Alkamuls ® GMS
Glycerol ester
Glycerol stearate
Rhodia HPCII


Kemester ® 1000
Glycerol trioleate
Glycerol trioleate
Crompton Corp.


Alkamuls ® EGDS
Glycol ester
Glycol distearate
Rhodia HPCII


Alkamuls ® JK
Guerbet ester
Guerbet diester
Rhodia HPCII


Neustrene ® 059
Hydrogenated tallow glycerol
(30% Palmitic, 60% Stearic)
Crompton Corp.


Neustrene ® 064
Hydrogenated tallow glycerol
(88% Stearic, 10% Palmitic)
Crompton Corp.


Miranol ® C2M-SF
Imidazoline derivative
Disodium Cocoampho
Rhodia HPCII




Dipropionate


Miranol ® JEM
Imidazoline derivative
Sodium Mixed C8
Rhodia HPCII




Amphocarboxylate


Antarox ® 724/P
Ethoxylate

Rhodia HPCII


Rhodacal ® N
Naphthalene Formaldehyde
Sodium Naphthalene
Rhodia HPCII



Sulfonates
Formaldehyde Sulfonate


Supragil TM WP
Naphthalene Sulfonates
Sodium Diisopropyl Naphthalene
Rhodia HPCII




Sulfonate


Alkamuls ® EL-620
PEG Ester
PEG-30 Castor Oil (ricinoleic +
Rhodia HPCII




oleic + palmitic . . . )


Duraphos ® 2EHA PO4
Phosphate Ester
Phosphoric Acid, Mono & Di(2-
Rhodia HPCII




ethylhexyl) ester


DEHPA ® extractant
Phosphate Ester
Phosphoric Acid, Bis(2-ethylhexyl)
Rhodia HPCII




ester


Rhodafac ® LO-11A LA
Phosphate Ester
Phosphoric Acid, Blend of linear
Rhodia HPCII




octyl/decyl alcohol esters


Amgard ® TOF
Phosphate Ester
Phosphoric Acid, Tris(2-ethylhexyl)
Rhodia HPCII




ester


Albrite ® B(2EH) 2EHP
Phosphonate Ester
Phosphonic Acid, (2-ethylhexyl)-
Rhodia HPCII




bis(2-ethylhexyl) ester


Octylphosphonic Acid
Phosphonate Ester
Octyl Phosphonic Acid Ester
Rhodia HPCII


Rhodaquat ® DAET-90
Quaternary Amine
Complex ditallow sulfate
Rhodia HPCII




quaternary amine


Alkamuls ® SML
Sorbitan ester
Sorbitan Monolaurate
Rhodia HPCII


Alkamuls ® SMO
Sorbitan ester
Sorbitan Monooleate
Rhodia HPCII


Alkamuls ® STO
Sorbitan ester, ethoxylated
Sorbitan Trioleate
Rhodia HPCII


OT-75, OT-100
Sulfosuccinates
Dioctyl sodium sulfosuccinate
Cytec









The components, UHMWPE, filler (optional), processing oil, and lubricant, are mixed. In formulations with filler, the weight ratio of polymer to filler may range from 1:1 to 1:5, 1:3 being preferred. The ratio of UHMWPE and filler to oil may range from 1:1 to 1:2, 1:1.5 being preferred. The lubricant may comprise up to 15 weight % of the formulation, with 0.2 to 8% being preferred. In formulation without filler, the polymer may comprise up to 80% by weight of the mixture, preferably in the range of 20-65% by weight. The ratio of oil to lubricant may range from 3:1 to 1:3, with the range of 2:1 to 1:2 being preferred. The components are preferably mixed in a continuous fashion, for example, in a twin screw extruder or a Brabender extruder or a screw extruder with a blown film die.
After mixing, the mixture is shaped. Shaping will depend upon the particular article desired, as is known in the art. For example, if a film or sheet is desired, then the appropriate die may be added to the extruder. After shaping, the articles are most often subjected to a step to remove the processing oil or solvent from the article (gel), (e.g., an extraction (or washing or leaching) step to remove processing oil and lubricant). This step is conventional. For example, see U.S. Pat. Nos. 3,351,495; 4,588,633; 4,833,172; 5,248,461; and 5,948,557 each is incorporated herein by reference. In formulations with filler, the extruded sheets are preferably subjected to an extraction step to remove processing oil. After extraction, these sheets may have about 0.5% (nominally 0%) to 30% by weight oil remaining, preferably 5-25%, and most preferably 10-20%. It is understood that it is impossible to remove all of the processing oil and lubricant from any of the mixtures, so at least a trace amount will remain in the final articles. In formulations without fillers, the extruded sheets are preferably subjected to an extraction step. After extraction, these sheets may have only residual amounts of oil and lubricant. Articles may be subjected to stretching or tentering before, during, or after extraction.
Preferably, these articles are formed into microporous sheets or films. Such microporous sheets and films may be used as labels, diffusion membranes, and separators in electrochemical devices (e.g., batteries, capacitors, and fuel cells). A battery is an electrochemical device having an anode, a cathode, an electrolyte, and a separator sandwiched between the anode and the cathode and impregnated with the electrolyte. Formulation with filler are used preferably in lead acid batteries. Formulations without filler are used preferably in lithium batteries.
EXAMPLES
In the following examples, set out in Tables 1-8, ultrahigh molecular weight polyethylene (GUR 4130 and GUR 4170 from Ticona LLC of Summit, N.J.), filler (specifically silica, HiSil from PPG of Pittsburgh, Pa.), processing oil (naphthalenic oil from Calumet Co. of Princeton, La.), and lubricant (as identified in the tables) were blended together and extruded from a twin screw extruder. The extruded product, a sheet, was subjected to an extraction step for the removal of processing oil. During extrusion, torque (% Kw) and melt temperature were measured for comparison to control (examples without additive) and indicates the amount of energy needed to mix the components. After extraction, the amount of oil remaining in the article of manufacture (final oil %) was determined by a extraction technique in which: a dried, 1.33 inch (3.38 cm)×6 inch (15.24 cm) piece of sheet was weighed (W1) and then immersed in 200 ml of fresh, room temperature hexane in a ultrasonic bath for at least 15 minutes; then the sample is dried and reweighed (W2). The % oil is [(W1-W2)/W1]*100. Two samples are averaged. Additionally, basis weight was measured in conventional fashion, and thickness (web) by ASTM D 374, MD tensile by ASTM D 638, porosity by Battery Council International (BCI) TM-3.207, and ER by BCI TM-3.218 using a conventional tester from Palico Instrument Limited of Circle Pines, Minn. Puncture strength generally follows ASTM D3763 except as noted below: The instrument used was a Chatillon digital force guage DFIS 10 on a motorized test stand TCM 201. Chatillon/Ametek is located in Largo, Fla. The puncture tip is slightly rounded and 1.930 mm in diameter, and the platform hole is 6.5 mm in diameter. The travel speed is set at 300 mm/min, and at least 10 measurements are averaged across a representative area of the sample. This method is generally independent of sample size, and representative area of the sample refers to across the width and length of a reasonably sized sample. The peak force needed to puncture the sample is recorded in units of N or lbs.
In Tables 1-5, ingredients were mixed at the throat of the extruder, and in Tables 6-8, the lubricant was injected through the extruder's barrel.









TABLE 1









Examples
















1
2
3
4
5
6
7
8




















Additive name


A
B
C
D
E
F
G


Polymer type

4170
4170
4170
4170
4170
4170
4170
4170


Polymer
kg
4.14
4.14
4.14
4.14
4.14
4.14
4.14
4.14


Filler
kg
10.76
10.76
10.76
10.76
10.76
10.76
10.76
10.76


Additive
kg
0.00
1.09
1.09
1.09
1.09
1.09
1.09
1.09


Oil
kg
27.50
26.41
26.41
26.41
26.41
26.41
26.41
26.41


Torque
% KW
26
24
25
27
24
25
26
24


Melt Temp.
° C.
210
214
214
216
208
268
208
212


Web Thickness
microns
189.2
217.2
220.0
209.8
208.0
206.2
205.5
203.2


Basis Weight
g/m2
106.9
140.0
140.9
127.1
134.1
129.4
134.0
127.0


Puncture
N
11.9
24.3
23.6
24.2
17.8
20.0
19.2
16.8


MD Tensile
N/mm2
17.5
28.9
29.1
29.3
27.3
21.9
26.4
21.6


Porosity
%
63.1
60.2
60.1
61.9
65.6
63.2
59.0
61.1


ER w/o Coating
mohm-cm2
582.6
285.2
279.4
285.2
385.2
505.8
705.8
541.3


Final Oil
%
18.2
13.9
14.1
15.2
14.9
16.7
14.5
19.7


















TABLE 2









Examples
















9
10
11
12
13
14
15
16




















Additive name


A
B
C
D
E
F
G


Polymer type

4130
4130
4130
4130
4130
4130
4130
4130


Polymer
kg
4.14
4.14
4.14
4.14
4.14
4.14
4.14
4.14


Filler
kg
10.76
10.76
10.76
10.76
10.76
10.76
10.76
10.76


Additive
kg
0.00
1.09
1.09
1.09
1.09
1.09
1.09
1.09


Oil
kg
27.50
26.41
26.41
26.41
26.41
26.41
26.41
26.41


Torque
% KW
28
24
26
27
25
28
25
26


Melt Temp.
° C.
207
211
214
214
203
216
214
221


Web Thickness
microns
179.1
232.2
227.3
211.3
172.0
209.6
202.4
229.4


Basis Weight
g/m2
106.6
147.8
139.9
131.8
112.9
135.3
132.1
144.7


Puncture
N
11.8
20.4
21.0
17.0
14.2
16.6
15.9
14.8


MD Tensile
N/mm2
18.3
24.8
21.9
23.1
21.9
19.1
22.6
16.9


Porosity
%
67.2
60.7
63.7
63.0
61.6
63.6
60.6
62.2


ER w/o Coating
mohm-cm2
461.3
240.0
263.2
283.2
163.2
361.3
362.6
471.6


Final Oil
%
23.8
13.4
15.6
13.7
22.8
14.7
14.3
13.7


















TABLE 3









Examples














17
18
19
20
21
22


















Additive name


A
B
C
F
H


Polymer type

4170
4170
4170
4170
4170
4170


Polymer
kg
3.10
3.10
3.10
3.10
3.10
3.10


Filler
kg
8.41
8.41
8.41
8.41
8.41
8.41


Additive
kg
0.00
0.82
0.82
0.82
0.82
0.82


Oil
kg
20.35
19.52
19.52
19.52
19.52
19.52


Torque
% KW
27
24
24
24
26
22


Melt Temp.
° C.
208
211
210
211
210
208


Web Thickness
microns
173.0
161.5
177.8
180.1
177.8
191.3


Basis Weight
g/m2
111.7
119.6
107.3
123.5
126.3
140.3


Puncture
N
11.4
16.2
13.6
16.0
13.2
20.3


MD Tensile
N/mm2
20.3
34.5
18.4
24.2
20.6
26.5


Porosity
%
59.2
58.1
59.7
60.7
59.7
59.1


ER w/o Coating
mohm-cm2
434.8
127.7
145.8
248.4
435.5
76.1


Final Oil
%
14.0
13.7
13.9
13.7
12.9
12.8


















TABLE 4









Examples













17
23
24
25
40

















Additive



A
H
A


name


Polymer

4170
4130
4170
4170
4170


type


Polymer
kg
3.10
3.10
2.87
2.87
4.39


Filler
kg
8.41
8.41
9.20
9.20
11.86


Additive
kg
0.00
0.82
1.63
1.63
1.12


Oil
kg
20.35
20.35
18.78
18.78
26.99


Torque
% KW
27
24
23
23
23


Melt Temp.
° C.
208
209
211
208
216


Web
mi-
173.0
177.8
180.3
172.7
114.3


Thickness
crons


Basis
g/m2
111.7
113.3
135.4
137.4
83.8


Weight


Puncture
N
11.4
10.1
13.5
17.5
11.4


MD
N/mm2
20.3
16.9
21.6
32.8
27.1


Tensile


Porosity
%
59.2
62.3
59.0
58.5
65.5


ER w/o
mohm-
434.8
464.5
78.1
64.5
36.1


Coating
cm2


Final Oil
%
14.0
14.6
12.5
11.6
14.7


















TABLE 5









Examples














26
31
27
28
29
30


















Additive name



I
J
K
K


Polymer type

4130
4170
4170
4170
4170
4170


Polymer
kg
3.10
4.39
3.10
3.10
4.34
3.25


Filler
kg
8.41
11.86
8.41
8.41
11.75
8.81


Additive
kg
0.00
0.00
0.82
0.82
0.53
0.82


Oil
kg
20.35
28.66
19.52
19.52
27.86
20.48


Torque
% KW

28
23
23
24
25


Melt Temp.
° C.

217
217

222
227


Web Thickness
microns
188.5
183.4
192.8
179.6
198.9
191.5


Basis Weight
g/m2
100.1
102.4
117.9
127.2
114.6
116.7


Puncture
N
9.6
13.1
16.8
22.0
11.5
12.8


MD Tensile
N/mm2
15.6
20.4
28.4
33.2
12.8
12.5


Porosity
%
63.0
66.3
62.5
61.1
66.2
65.9


ER w/o Coating
mohm-cm2
320.3
221.9
109.8
397.4
292.3
220.0


Final Oil
%
13.7
10.9
11.2
11.5
11.9
12.5


















TABLE 6









Examples














31
32
33
34
35
41


















Additive name


J
J
J
J
J


Polymer type

4170
4170
4170
4170
4170
4170


Polymer
kg
4.39
4.39
4.39
4.39
4.39
3.35


Filler
kg
11.86
11.86
11.86
11.86
11.86
9.04


Additive
kg
0.00
0.55
1.12
2.32
3.59
1.63


Oil
kg
28.66
27.83
26.99
25.25
23.42
23.59


Torque
% KW
28
28
26
24
25
24


Melt Temp.
° C.
217
210
207
205
204
204


Web Thickness
microns
183.4
175.3
182.9
162.6
170.2
182.9


Basis Weight
g/m2
102.4
119.2
122.2
126.0
141.2
118.5


Puncture
N
13.1
15.2
20.8
22.5
24.5
17.1


MD Tensile
N/mm2
20.4
24.3
38.2
48.8
48.5
22.1


Porosity
%
66.3
65.3
61.4
58.1
57.0
61.1


ER w/o Coating
mohm-cm2
221.9
198.7
282.6
1052.9
751.6
543.9


Final Oil
%
10.9
12.8
12.5
13.9
13.3
13.8


















TABLE 7









Examples













31
36
37
38
39

















Additive


H
H
H
H


name


Polymer

4170
4170
4170
4170
4170


type


Polymer
kg
4.39
4.39
4.39
4.39
4.39


Filler
kg
11.86
11.86
11.86
11.86
11.86


Additive
kg
0.00
0.55
1.12
2.32
3.59


Oil
kg
28.66
27.83
26.99
25.25
23.42


Torque
% KW
28
25
24
26
27


Melt
° C.
217
213
201
200
204


Temp.


Web
mi-
183.4
170.2
182.9
183.6
167.6


Thickness
crons


Basis
g/m2
102.4
108.2
152.2
145.4
156.4


Weight


Puncture
N
13.1
12.9
22.5
16.4
14.8


MD
N/mm2
20.4
21.3
46.7
38.3
33.4


Tensile


Porosity
%
66.3
64.4
61.2
61.1
57.0


ER w/o
mohm-
221.9
46.5
223.9
593.5
150.3


Coating
cm2


Final Oil
%
10.9
14.1
12.9
13.8
12.5


















TABLE 8









Examples
















49
42
43
44
45
46
47
48




















Additive name


L
M
N
O
P
Q
R


Polymer type

4170
4170
4170
4170
4170
4170
4170
4170


Polymer
Kg
3.25
3.25
3.25
3.25
3.25
3.25
3.25
3.25


Filler
Kg
8.79
8.79
8.79
8.79
8.79
8.79
8.79
8.79


Additive
Kg
0.00
0.82
0.82
0.82
0.82
0.82
0.82
0.82


Oil
Kg
21.27
20.34
20.34
20.34
20.34
20.34
20.34
20.34


Torque
% KW
24
24
24
24
23
24
23
24


Melt Temp.
° C.
227
234
233
236
235
234
234
237


Web Thickness
microns
157.5
177.8
167.6
175.3
185.4
162.6
180.3
175.3


Basis Weight
g/m2
110.6
126.3
120.0
125.0
129.4
119.4
119.4
125.6


Puncture
N
10.6
18.5
15.9
18.5
16.4
17.5
13.8
17.4


MD Tensile
N/mm2
16.3
34.8
31.9
45.7
31.6
35.8
33.1
35.8


Porosity
%
64.5
61.6
62.5
63.0
63.4
61.7
63.0
63.7


ER w/o Coating
mohm-cm2
470.3
872.9
1707.1
201.3
376.1
225.2
294.8
19.4


Final Oil
%
13.6
12.5
12.7
14.3
14.0
14.8
15.5
14.3









In the following examples, set out in Table 9, ultrahigh molecular weight polyethylene (GUR 4130 from Ticona LLC of Summit, N.J.), processing oil (naphthalenic oil from Calumet Co. of Princeton, La.), and lubricant (as identified in the table) were blended together and extruded from a twin screw extruder. The extruded product was observed as it exited the extruder die and categorized by appearance scale 1-10. A rating of 10 meant a smooth product that appeared well mixed, and a rating of 1 meant a very grainy and rough appearance.









TABLE 9









Examples:


















46
47
48
49
50
51
52
53
54
55





















polymer wt %
33.0
38.5
52.9
38.5
52.2
50.0
45.0
61.0
25.0
65.0


oil wt %
33.0
46.1
17.7
38.5
23.9
35.0
20.0
14.0
50.0
12.7


additive wt %
33.0
15.4
29.4
23.0
23.9
15.0
35.0
25.0
25.0
22.3


name additive
J
J
J
J
J
J
J
J
J
J


VISUAL RATING
5
6
8
8
9
4
1
10
10
4









    A=Phosphate Ester; fatty alcohol blend phosphate esters; Rhodafac LO-11A LA from Rhodia HPCII of Cranberry, N.J.
    B=Phosphate Ester; Bis(2-ethylhexyl)phosphate ester from Rhodia HPCII of Cranberry, N.J.
    C=Phosphate Ester; Bis(2-ethylhexyl)+mono(2-ethylhexyl) phosphate esters from Rhodia HPCII of Cranberry, N.J.
    D=Phosphonate Ester; 2-ethylhexyl bis(2-ethylhexyl)phosphonate ester from Rhodia HPCII of Cranberry, N.J.
    E=Phosphate Ester; Tris(2-ethylhexyl)phosphate ester from Rhodia HPCII of Cranberry, N.J.
    F=Fatty acids, unsaturated; linoleic and linolenic acids; Linseed Oil.
    G=Fatty acids, unsaturated; eleostearic acid; Tung Oil.
    H=Phosphonate Ester; octyl phosphonic acid ester from Rhodia HPCII of Cranberry, N.J.
    I=PEG Esters; PEG-30 castor oil (ricinoleic+oleic+palmitic . . . ); Alkamuls EL-620 from Rhodia HPCII of Cranberry, N.J.
    J=Sorbitan Esters; sorbitan monooleate; Alkamuls SMO from Rhodia HPCII of Cranberry, N.J.
    K=Sulfosuccinate Ester; dioctyl sodium sulfosuccinate; OT-100 from Cytec Industries of Charlotte, N.C.
    L=Sorbitan Ester; sorbitan monolaurate; Alkamuls SML from Rhodia HPCII of Cranberry, N.J.
    M=Sorbitan Ester Ethoxylated; sorbitan trioleate; Alkamuls STO From Rhodia HPCII of Cranberry, N.J.
    N=Aromatic Ethoxylate; dodecyl phenol ethoxylates; lgepal RC-630 From Rhodia HPCII of Cranberry, N.J.
    O=Aromatic Ethoxylate; nonylphenol ethoxylates; lgepal CO-210 From Rhodia HPCII of Cranberry, N.J.
    P=Aromatic Ethoxylate; nonylphenol ethoxylates; lgepal CO-630 From Rhodia HPCII of Cranberry, N.J.
    Q=Alcohol Ethoxylate; mixed linear alcohol ethoxylates; Rhodasurf LA-3 from Rhodia HPCII of Cranberry, N.J.
    R=Alcohol Ethoxylate; mixed linear alcohol ethoxylates; Rhodasurf LA-12 from Rhodia HPCII of Cranberry, N.J.


In the following examples, set out in Table 10, ultrahigh molecular weight polyethylene (GUR 4170 from Ticona LLC, Summit, N.J.), filler (silica, HiSil from PPG of Pittsburgh, Pa.), processing oil (naphthelenic oil from Calumet Co. of Pamaton, La.), and lubricant (as identified in the table) were mixed together and extruded from a Brabender extruder (BW Brabender Co. of South Hackensack, N.J.). In the control, 5.42 grams of UHMWPE was mixed with 14.65 g filler and 30.56 g oil. In the other examples, 5.42 grams of UHMWPE was mixed with 14.65 filler, 29.06 g oil and 1.50 g lubricant. This procedure is used to predict the lubricant's efficacy by observing fusion time and terminal torque. The fusion time is a measure of when the polymer dissolves in the oil (phase inversion of the polymer). The fusion time is typically the second peak on a plot of torque as a function of time. The fusion time typically occurs after a first peak which indicates wetting of the polymer by the oil. The terminal torque is measured after 10 minutes of mixing.











TABLE 10








Fusion Time
Terminal



Additive
(sec)
Torque (mg)




















Control - 59% Oil
182
660



Octyl PO4
42
501



Antarox 724/P
48
685



Alkamide STEDA/B
55
845



Rhodasurf LA-12
61
633



T(2EH)PO4
64
640



Alkamuls SMO
65
566



Igepal CO-630
66
627



Alkamuls STO
66
553



Alkamuls SML
71
607



Rhodasurf LA-3
74
545



Alkamuls EL-620
83
583



Igepal CO-210
88
528



Igepal RC-630
92
601



Linseed Oil
92
650



B(2EH)2EHP1
92
610



2EHAPO4
95
465



DEHPA
100
410



Rhodafac LO-11A
109
516



Rhodapon BOS
110
623



Tung Oil
114
647



OT-75
115
820



Rhodapex CD-128
122
570



Miranol C2M-SF
125
678



Mirataine COB
135
730



Mirataine CBS
135
752



Miranate LEC-80
140
672



Miranol JEM
149
727



Rhodapon UB
152
892



Supragil WP
153
776



Ca Stearate
196
766



Rhodacal N
230
816



Neustrene 059



Neustrene 064



Kemester 1000



Rhodaquat DAET-90



Rhodameen PN-430



Rhodameen T-50



Alkamuls GMS



Alkamuls EGDS



Alkamuls JK










The present invention may be embodied in other forms without departing from the spirit and the essential attributes thereof, and, accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicated the scope of the invention.

## Claims

1. An article of manufacture comprising:
an ultrahigh molecular weight polyethylene (UHMWPE) mixed with a filler, a processing oil, and a lubricant selected from the group consisting of: aromatic ethoxylated esters, mercaptan ethoxylates, phosphonate esters, alkylaryl ether sulfates, naphthalene sulfonates, sulfonated esters, alkylaryl ether carboxylates, amino quaternary amines, imidazoline derivatives, sultaines, aminopropionate, catechol derivatives, and combinations thereof, said lubricant is present in an amount from 0.2% to 15% by weight.

2. The article of manufacture of claim 1 wherein said lubricant is selected from the group consisting of: aromatic ethoxylated esters, phosphonate esters and combinations thereof.

3. The article of manufacture of claim 1 wherein a weight ratio of said ultrahigh molecular weight polyethylene to said filler ranges from 1:1 to 1:5.

4. The article of manufacture of claim 1 wherein said ultrahigh molecular weight polyethylene has a weight average molecular weight greater than 2×106.

5. A battery separator comprising a microporous membrane comprising the article of claim 1.

6. The battery separator of claim 5 wherein said battery is a lead acid battery.

7. An article of manufacture comprising:
an ultrahigh molecular weight polyethylene (UHMWPE) having a weight average molecular weight greater than 5×106, mixed with a filler, a processing oil, and a lubricant selected from the group consisting of aromatic ethoxylated esters, mercaptan ethoxylates, phosphonate esters, alkylaryl ether sulfates, naphthalene sulfosuccinates, alkylaryl ether carboxylates, amino quaternary amines, imidazoline derivatives, sultaines, aminopropionate, catechol derivatives, and combinations thereof, said lubricant is present in an amount from 0.2% to 15% by weight.

8. The article of manufacture of claim 7 wherein said lubricant is selected from the group consisting of: aromatic ethoxylated esters, phosphonate esters and combinations thereof.

9. The article of manufacture of claim 7 wherein a weight ratio of said ultrahigh molecular weight polyethylene to said filler ranges from 1:1 to 1:5.

10. A battery separator comprising a microporous membrane comprising the article of claim 7.

11. The separator of claim 10 wherein said battery is a lead acid battery.