~ " ' MM II II II Ml II I Mill II II II I II

J European Patent Office __ _

© Publication number: 0 287 092 B1
_„.
Office europeen des brevets

© EUROPEAN PATENT SPECIFICATION

© Date of publication of patent specification: 03.11.93 © Int. CI.5: C08L 101/00, //(C08L1 0 1 / 0 0 ,
71 :02)
© Application number: 88105947.1

@ Date of filing: 14.04.88

© Antistatic Polymer Composition and Production thereof.

© Priority: 17.04.87 US 39258 © Proprietor: The B.F. Goodrich Company

3925 Embassy Parkway
@ Date of publication of application: Akron Ohio 4431 3(US)
19.10.88 Bulletin 88/42
@ Inventor: Yu, Simon Hslao-Pao
© Publication of the grant of the patent: 1812 Farr's Garden Path
03.11.93 Bulletin 93/44 Westlake Ohio 441 45(US)

© Designated Contracting States:

AT BE CH DE ES FR GB GR IT LI LU NL SE © Representative: von Krelsler, Alek,
Dlpl.-Chem. et al
© References cited: Patentanwalte
CH-A- 352 828 Von Krelsler-Seltlng-Werner,
US-A- 3 329 557 Postfach 10 22 41,
US-A- 4 379 913 Bahnhofsvorplatz 1
D-50462 Koln (DE)
CHEMICAL ABSTRACTS, vol. 101, 1984, page
42, abstract no. 131705k, Columbus, Ohio,
US; L.Kh. GARIFOVA et al.: "Reducing the
static charge of polyvinyl chloride) films
using certain plasticizers", & POLIM.
STROIT. MATER. 1983, 12-13
00
CM
Oi

00
CM
Note: Within nine months from the publication of the mention of the grant of the European patent, any person
may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition
shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee
has been paid (Art. 99(1) European patent convention).
Rank Xerox (UK) Business Services
(3. 10/3.6/3.3. 1)
 EP 0 287 092 B1

Description

BACKGROUND OF THE INVENTION

5 1) Field of the Invention

The present invention relates to a new class of antistatic additives based on solid copolymers of
ethylene oxide having a high molecular weight. When used with plastics as an antistatic additive, thus
forming the antistatic polymeric composition as claimed, the ethylene oxide copolymers do not significantly
io impair the physical properties of the plastic. The ethylene oxide copolymers are also stable at high
processing temperatures and do not cause blooming of the finished product (oiliness, crazing, marblizing,
and cracking). The present invention also relates to a process for preparing an antistatic polymeric
composition.

75 2) Prior Art

The retention and amplification of charges of static electricity on the surface of most plastics is well
known. Plastic materials have a significant tendency to accumulate static electrical charges due to low
electrical conductivity. A sudden discharge of static electrical charges in the form an electric arc is a fire
20 hazard and exposes personnel handling the processed plastic to electrical shock. Furthermore, the
presence of static electrical charges on sheets of thermoplastic film, for example, can cause the sheets to
adhere to one another thus making their separation for further processing more difficult. Moreover, the
presence of static electrical charges causes dust to adhere to items packaged in a plastic bag, for example,
which may negate any sales appeal.
25 The increasing complexity and sensitivity of microelectronic devices makes the control of electrostatic
discharge (ESD) of particular concern to the electronic industry. Only a few hundred volts can cause
damage to sensitive devices and result in disappointing manufacturing yields, erratic errors, transient
malfunctions, erased memory, etc. The need to control ESD requires the total assembly environment to be
constructed of partially conductive materials. It also requires electrostatic protective packages, tote boxes,
30 casings, and covers to store, ship, protect, or support electrical devices and equipment made from
polymeric materials possessing antistatic properties. Additionally, accumulation of static electrical charges
on electrical equipment like computers or vacuum cleaners or on finished goods such as carpet can cause
the electrical equipment to fail or cause carpet to transfer accumulated static charges to the user during
periods of low humidity.
35 To prevent static electrical charges from accumulating during manufacturing of the plastic, during
forming of articles of manufacture, and during the useful life of the various articles of manufacture, it is well
known to employ various types of antistatic agents. The antistatic agents can take the form of a coating
which may be sprayed upon the manufactured sheets of plastic or the article of manufacture, for example,
but this solution is often temporary.
40 Other attempts to overcome the static charges call for incorporating an antistatic agent into the plastic
during processing in order to provide a more "permanent" antistatic characteristic to the manufactured
plastic, articles of manufacture made from the plastic, etc.. However, the incorporation of antistatic agents
into the various types of plastics have created other problems. For example, a majority of the antistatic
agents cannot withstand high temperatures and they are destroyed or rendered useless with respect to their
45 antistatic abilities during the hot temperature processing required in conventional moding or fabricating
steps for forming articles of manufacture. This limits their applications to low-melting plastics, such as low
density polyethylenes.
A majority of the antistatic agents are also either cationic or anionic. They tend to cause the
degradation of plastics, particularly PVC and polyacetals, at hot processing temperatures resulting in
50 discoloration or loss of physical properties. Other antistatic agents have significantly lower molecular
weights than the polymers themselves. Generally, lower molecular weight antistatic agents possess
undesirable lubricating properties and are difficult to incorporate into the polymer. Incorporation of the lower
molecular weight antistatic agents into the polymers often reduce the moldability of the plastic because the
antistatic agents bleed through to the surface of the plastic and frequently deposit a coating on the surface
55 of the molds, thus destroying the surface finish on the articles of manufacture and reduce the dimensional
stability when exposed to heat. In severe cases, the surface of the article of manufacture becomes quite oily
and marblized. This is called blooming. Additionally, the lower molecular weight antistatic agents often tend
to lose their antistatic capability due to evaporation, develop undesirable odors, and promote cracking or

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 EP 0 287 092 B1

crazing on the surface of the article of manufacture.

One of the known lower molecular weight antistatic agents is a homopolymer or copolymer of ethylene
oxide. Generally, the lower molecular weight polymers of ethylene oxide antistatic agents are subject to the
above mentioned problems relative to lubricity, blooming, or less effective antistatic properties. Exemplary
5 of the lower molecular weight antistatic agents comprising a homopolymer of ethylene oxide are Carbowax®
by Union Carbide; Polyglycol® E by Dow Chemical, Pluracol® E by BASF Wyandotte, and U.S. Patents
4,274,986; 3,745,116; and 3,625,915. Exemplary of the lower molecular weight antistatic agents comprising
a block copolymer of ethylene oxide and propylene oxide are: Pluronic® by BASF Wyandotte; Voranol® by
Dow Chemical; U.S. Patent 3,686,120; Japanese Patents 49-23,246; 48-66,648; and 47-8,776; and German
io Patents 2,214,219 and 2,127,654. Exemplary of lower molecular weight antistatic agent comprising a
random copolymer of ethylene oxide and propylene oxide are: Ucon® by Union Carbide; and U.S. Patent
3,686,120 which is directed to external surface treatment.
Prior to the present invention, conventional thinking was that high molecular weight copolymers of
ethylene oxide would significantly impair the physical properties of the plastic. Moreover, prior thinking was
is that a high molecular weight antistatic agent does not have good antistatic qualities and characteristics. In
fact, prior art indicates that a molecular weight above about 20,000 to 25,000 is definitely undesirable.
Exemplary of such prior art are U.S. Patents 3,686,120 and 4,274,986.
The art of use high molecular weight ethylene oxide homopolymers have been described in U.K. Patent
Application 2,139,230 and Japanese Patent 60-206,856. However, high molecular weight ethylene oxide
20 homopolymers are difficult to incorporate into other polymeric materials probably due to the high crystal-
linity of homopolymers. Furthermore, homopolymers are uneffective antistatic agents when incorporated into
polymeric materials at small amounts. When larger amounts of homopolymers are incorporated, the
antistatic properties of polymeric materials are slightly improved, but the materials become extremely
brittle.
25 The use of high molecular weight ethylene oxide polymers, including copolymers, for olefin polymers
as antistatic additives has been disclosed in U.S. Patent 3,425,981 to Puletti and Gardner. Poly(ethylene
oxide) homopolymer is the preferred antistatic agent. The patent discloses that the antistatic agent is
incorporated only into olefin polymer compositions. The patent fails to indicate the significant advantages of
copolymers over homopolymers of ethylene oxide. Furthermore, the patent also fails to indicate the wide
30 applications of antistatic copolymers to a variety of polymeric materials. The copolymers of ethylene oxide
of this invention fail to show significant antistatic improvement when applied to any olefin polymer
compositions such as polyethylene. When a copolymer of this invention comprising 85 weight percent of
ethylene oxide and 15 weight percent of propylene oxide was incorporated at 10 weight parts per 100
weight parts of polyethylene, both low density polyethylene (Escorne® LD 405-49 from Exxon) and high
35 density polyethylene (Amoco 3250B from Amoco) gave a surface resistivity greater than 101G ohm/sq, which
is classified as an insulator. According to the teaching of U.S. Patent 3,425,981, the copolymers of ethylene
oxide of the present invention will be useless as antistatic additives.
Various copolymers of ethylene oxide having a high molecular weight are taught by the prior art. For
example, German Patent 1,109,901 discloses a copolymer of ethylene oxide and propylene oxide which is
40 formed by contacting the monomers with a coordination catalyst based on triethylaluminum (TEAL).
Although the German patent does not disclose that these high molecular weight compounds can be used as
antistatic agents, it does mention that the high molecular weight compounds can be utilized as thickeners
and as a film base.
It is an objective of the present invention to provide an antistatic polymeric composition consisting of:
45 a) at least one antistatic additive of an ethylene oxide copolymer in the range of from 3 to 30% by
weight, said antistatic ethylene oxide copolymer being a nonionic solid material at room temperature
having a dilution solution viscosity of greater than 0.25 g/ml
as determined on a solution made up with 0.25 grams of the polymer in 100 grams of toluene with
capillary viscometer at 25 °C according to ASTM D2857, said copolymer excluding epihalohydrin; and
50 b) a polymeric material selected from copolymers of styrene and acrylonitrile; terpolymers of styrene,
acrylonitrile, and diene rubber; copolymers of styrene and acrylonitrile modified with acrylate elastomers;
copolymers of styrene and acrylonitrile modified with ethylene propylene diene monomer rubber;
polystyrene and rubber modified impact polystyrene; polycarbonates; thermoplastic polyesters including
polybutylene terephthalate, polyethylene terephthalate and polyether-ester block copolymers; polyure-
55 thane; thermoplastic polyurethane; polyphenylene oxide; polyacetals; polymethyl methacrylate; and
mixtures thereof and their polymer blends in the range of from 70 to 97% by weight, wherein said
ethylene oxide copolymer comprises:
a) ethylene oxide in the range of from 5 to 95% by weight; and

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 EP 0 287 092 B1

b) at least one cyclic comonomer selected from an alkylene oxide containing up to 25 carbon atoms
represented by the formula:

wherein, Ri , R2, R3, and R+ are selected from hydrogen, saturated aliphatic, cycloaliphatic, monoolefinic
aliphatic and cycloaliphatic, diolefinic (conjugated and non-conjugated) aliphatic and cycloaliphatic,
aromatic, and aralkyl, alkaryl; and at least of R1 , R2, R3, and R+ is not hydrogen; said cyclic comonomer
15 is in the range of from 95 to 5% by weight of the total weight of said ethylene oxide copolymer;
said ethylene oxide copolymer having a weight average molecular weight from 20,000 to 5,000,000.
Said composition is stable at high temperatures, inert toward and compatible with plastics, and yet do
not cause blooming, do not develop undesirable odors, do not significantly impair physical properties and
produces a "permanent" antistatic material with a surface resistivity in the order 1010 to 1013 ohms per
20 square depending on the amount of antistat incorporated,.
It is another objective of the present invention to provide a process of preparing an antistatic polymeric
composition comprising:
a) adding polymeric material selected from copolymers of styrene and acrylonitrile; terpolymers of alpha-
methylstyrene and acrylonitrile and copolymers of styrene and acrylonitrile; diene rubber; copolymers of
25 styrene and acrylontrile modified with acrylate elastomers; copolymers of styrene and acrylonitrile
modified with ethylene propylenediene monomer rubber; polystyrene and rubber modified impact
polystyrene; polycarbonates, thermoplastic polyesters including polybutylene terephthalate, polyethylene
terephthalate and polyether-ester block copolymers; polyurethane; thermoplastic polyurethane; poly-
phenylene oxide; polyacetals; polymethyl methacrylate; and mixtures thereof and their polymer blends,
30 said polymeric material is in the range from 70 to 97% by weight of said antistatic polymeric
composition to an effective amount of solid antistatic additive consisting of an ethylene oxide copolymer
having a dilution solution viscosity of greater than 0.25, said copolymer excluding epihalohydrin; and
b) mixing said polymeric material and said ethylene oxide copolymer to produce an antistatic polymeric
composition, wherein said ethylene oxide copolymer comprises:
35 a) ethylene oxide in the range of from 5 to 95% by weight of the ethylene oxide copolymer; and
b) at least one cyclic comonomer in the range of from 95 to 5% by weight of the ethylene oxide
copolymer, selected from alkylene oxide containing up to 25 carbon atoms represented by the formula:

40

45

wherein R1 , R2, R3, and R+ selected from the group consisting of hydrogen, saturated aliphatic,
cycloaliphatic, monoolefinic aliphatic and cycloaliphatic, diolefinic (conjugated and non-conjugated)
50 aliphatic and cycloaliphatic, aromatic, and aralkyl, alkaryl; and at least one of R1 , R2, R3, and R+ is not
hydrogen,
said ethylene oxide copolymer having a weight average molecular weight from 20,000 to 5,000,000.
These and other objectives and advantages of the invention will become apparent by reference to the
following description.
55

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 EP 0 287 092 B1

SUMMARY OF THE INVENTION

The present invention concerns a solid, nonionic, high molecular weight copolymer of ethylene oxide
employed as an antistatic agent in various plastic compounds forming the antistatic polymeric composition
5 as claimed. In particular, the present invention concerns the combination of a high molecular weight
copolymer of ethylene oxide and a polymeric material such as terpolymer of acrylonitrile-butadiene-styrene
(ABS), polyamides, polyesters, and polycarbonates.
It is surprisingly found that by adding one or more cyclic comonomers to ethylene oxide, thus forming
the high molecular weight copolymers of this invention, significantly improves their antistatic performance.
io Furthermore, the copolymers are easily incorporated into polymeric material and do not impair the physical
properties of polymeric materials significantly. Additionally, the copolymers still maintain the advantages of
the nonionic nature of the homopolymers, which are stable at high processing temperatures and do not
cause the degradation of the polymeric materials.
Since the function of antistatic additives is believed to improve the conductivity by absorption of small
is quantities of moisture at the surface of polymeric material, it is expected that the performance of an anti
static additive should improve as it becomes more hydrophilic. The improvement of antistatic performance
by replacing some hydrophilic ethylene oxide units in the homopolymers with hydrophobic units to form
copolymers of the present invention is unexpected.
In the broadest sense, the present invention concerns an antistatic polymeric composition having an
20 effective amount of at least one antistatic additive of an ethylene oxide copolymer having a dilution solution
viscosity of greater than 0.25, the copolymer excluding epihalohydrin and a polymeric material. The
ethylene oxide copolymer is in the range of from 3 to 30% by weight; while the polymeric material is in the
range of from 70 to 97% by weight.
In the broadest sense, the present invention also concerns a process for preparing an antistatic
25 composition by adding to a polymeric material an effective amount of solid antistatic agent consisting of an
ethylene oxide copolymer having a dilution solution viscosity of greater than 0.25, the copolymer excluding
epihalohydrin; and mixing the polymeric material and the ethylene oxide copolymer to produce a uniform
antistatic polymeric composition.

30 DESCRIPTION OF THE PREFERRED EMBODIMENTS

A solid, nonionic copolymer of ethylene oxide which has a high molecular weight is useful as an
antistatic agent for various elastomers and plastics. By high molecular weight copolymer, it is meant
polymers is a solid at room temperature and having a DSV (dilution solution viscosity) of greater than 0.25
35 g/ml as determined on a solution made up with 0.25 grams of the polymer in 100 grams of toluene with
capillary viscometer at 25 °C according to ASTM D2857, therein referred to as inherent viscosity and
preferably having a weight average molecular weight greater than 20,000 as measured by gel permeation
chromatography, osmometry, cryoscopy, or ebullioscopy. Low molecular weight polymers referred to in the
present application generally is a viscous liquid at room temperature and have a weight average molecular
40 weight less than 20,000 and a DSV less than 0.25.
Copolymers of ethylene oxide with one or more cyclic monomers containing up to including 25 carbon
atoms per molecule may be suitable antistatic agents. Non-cyclic functional monomers cannot be used
because they cannot be copolymerized due to differences in functionality between cyclic and non-cyclic
monomers. Copolymers of ethylene oxide may be blocked, graft, random, or alternating copolymers, but
45 preferably random copolymers. The copolymers are high molecular weight with weight average molecular
weighs greater than 20,000 and in the range of from 20,000 to 5,000,000 as measured by gel permeation
chromatography, osmometry, cryoscopy, or ebullioscopy, or with a DSV value greater than 0.25 and in the
range of from 0.25 to 15.0. Preferably, the molecular weight is in the range of from 25,000 to 1,000,000, or
with a DSV value in the range of from 0.5 to 5.0. Because of the high molecular weight, copolymers of
50 ethylene oxide of the present invention are solid instead of viscous liquids. Accordingly, the solid
copolymers are easily handled, easily use with existing equipment and are easily incorporated into
polymeric materials.
In the copolymers of the present invention, the amount of ethylene oxide can vary from 5 to 95 weight
parts, whereas one or more of the comonomers used along with the ethylene oxide can vary in an amount
55 of from 95 to 5 weight parts. Particularly preferred copolymers consist of 40 to 95 weight parts of ethylene
oxide with 60 to 5 weight parts of one or more comonomers all on the basis of 100 weight parts.
The one or more comonomers of the present invention can be alkylene oxide containing up to 25
carbon atoms represented by the formula:

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 EP 0 287 092 B1

10 wherein Ri , R2, R3, and R+ are selected from the group consisting of hydrogen, saturated aliphatic and
cycloaliphatic, monoolefinic aliphatic, and cycloaliphatic, diolefinic (conjugated and non-conjugated) aliphatic
and cycloaliphatic, and aromatic, aralkyl, alkaryl and a like. Some or all of the R1 , R2, R3, and R+ can be
halogen-substituted, excluding epihalohydrin, and can contain oxygen in the form of ether linkages or an
ester linkage, or another oxirane group. In addition, both R1 and R3 can represent a divalent aliphatic
15 hydrocarbon radical which, together with the carbon atoms of the oxirane group can form a cycloaliphatic
hydrocarbon ring containing from about 4 to about 10 carbon atoms and preferably from 5 to 6 carbon
atoms. Finally, at least one of R1 , R2, R3, and R+ is not hydrogen.
Exemplary of the alkylene oxides which are represented by the above structural formula and which can
be copolymerized with ethylene oxides are: 1,2-epoxypropane(propylene oxide); 1,2-epoxybutane; 2,3-
20 epoxybutane(cis & trans); 1,2-epoxypentane; 2,3-epoxypentane(cis & trans); 1,2-epoxyhexane; 2,3-
epoxyhexane(cis & trans); 3,4-epoxyhexane (cis & trans); 1,2-epoxyheptane; 1,2-epoxydecane; 1,2-epox-
ydodecane; 1,2-epoxyoctadecane; 7-ethyl-2-methyl-1 ,2-epoxy epoxyundecane; 2,6,8-trimethyl-1 ,2-epox-
ynonane; styrene oxide. Typical alkylene oxide comprising cycloaliphatic hydrocarbon ring represented by
the above formula are: cyclohexene oxide; 6-oxabicyclo[3,1 ,0]-hexane; 7-oxabicyclo[4,1 ,0] heptane;
25 Typical halogen-substituted alkylene oxides represented by the above formula are: 3-chloro-1 ,2-
epoxybutane; 3-chloro-2,3-epoxybutane; 3,3-dichloro-1 ,2-epoxypropane; 3,3,3-trichloro-1 ,2-epoxypropane; 3-
bromo-1 -2-epoxybutane; 3-fluoro-1 ,2-epoxybutane; 3-iodo-1 ,2-epoxybutane; 1,1 -dichloro-1 -fluoro-2,3-epox-
ypropane; 1-chloro-1 ,1-dichloro-2,3-epxoypropane; and 1,1 ,1 ,2-pentachloro-3,4-epoxybutane.
Typical alkylene oxides with at least one ether linkage represented by the formula are exemplified by:
30 ethyl glycidyl ether; n-butyl glycidyl ether; isobutyl glycidyl ether; t-butyl glycidyl ether; n-hexyl glycidyl
ether; 2-ethylhexyl glycidyl ether; heptafluoroisopropyl glycidyl ether; phenyl glycidyl ether; 4-methyl phenyl
glycidyl ether; benzyl glycidyl ether; 2-phenylethyl glycidyl ether; 1,2-dihydropentafluoroisopropyl glycidyl
ether; 1,2-trihydrotetrafluoroisopropyl glycidyl ether; 1,1-dihydrotetrafluoropropyl glycidyl ether; 1,1-
dihydrononafluoropentyl glycidyl ether; 1,1-dihydropentadecafluorooctyl glycidyl ether; 1,1-
35 dihydropentadecafluorooctyl-a-methyl glycidyl ether; 1,1-dihydropentadecafluorooctyl-^-methyl glycidyl
ether; 1,1-dihydropentadecafluorooctyl-a-ethyl glycidyl ether; 2,2,2-trifluoro ethyl glycidyl ether.
Typical alkylene oxides with at least one ester linkage represented by the formula are: glycidyl acetate;
glycidyl chloroacetate; glycidyl butylrate; and glycidyl stearate; to name a few.
Typical unsaturated alkylene oxides represented by the formula are: allyl glycidyl ether; 4-vinyl-
40 cyclohexyl glycidyl ether; a-terpinyl glycidyl ether; cyclohexenylmethyl glycidyl ether; p-vinylbenzyl glycidyl
ether; allylphenyl glycidyl ether; vinyl glycidyl ether; 3,4-epoxy-1-pentene; 4,5-epoxy-2-pentene; 1,2-epoxy-
5,9-cyclododecadiene; 3,4-epoxy-1-vinylcyclohexene; 1,2-epoxy-5-cyclooctene; glycidyl acrylate; glycidyl
methacrylate; glycidyl crotonate; glycidyl 4-hexenoate.
Preferable alkylene oxides are those in which the R2, R3, and R+ radicals are hydrogen and the R1
45 radical being saturated aliphatic containing less than two ether linkages. The most preferable alkylene oxide
is propylene oxide.
Other cyclic monomers suitable to copolymerize with ethylene oxide are cyclic ethers with four or more
member-ring containing up to 25 carbon atoms except tetrahydropyran and its derivatives. Exemplary cyclic
ethers with four or more member-ring are oxetane (1 ,3-epoxide), tetrahydrofuran (1 ,5-epoxide), and oxepane
50 (1 ,6-epoxide) and their derivatives.
Other suitable cyclic monomers are cyclic acetals containing up to 25 carbon atoms. Exemplary cyclic
acetals are trioxane, dioxolane, 1,3,6,9-tetraoxacycloundecane, trioxepane, trioxocane, dioxepane, and their
derivatives.
Other suitable cyclic monomers are cyclic esters containing up to 25 carbon atoms. Exemplary cyclic
55 esters are beta-valerolactone, epsilon-caprolactone, zeta-enantholactone, eta-caprylactone, butyrolactone
and their derivatives.
Antistatic copolymers of ethylene oxide may be used together with other suitable known antistatic
agents including long chain amines, ethers, and esters, amides; salts of quaternary ammonium and sulfonic

6
 EP 0 287 092 B1

acids and alkyl, aryl or alkylaryl sulfonates and phosphoric acids; alkyl, aryl, or alkylaryl phosphates;
especially their ethoxylate derivatives; and low molecular weight polyether glycols.
Other additives may also be incorporated to improve the performance of the plastics, including fillers,
reinforcements, impact modifiers, heat distortion improvers, processing aids, plasticizers, anti-oxidants,
5 thermal stabilizers, pigments, color agents, ultraviolet-light stabilizers, flame retardants, lubricants, slip
agents, and blowing agents.
The polymerization process for epoxides in general is already known in the art. Generally, one or more
epoxide and the catalyst are contacted in the presence of an inert diluent. Further detailed description of the
polymerization process may be found by reference to U.S. Patents 3,186,958; 3,640,908; 3,657,159; and
io 3,135,705.
Any epoxide polymerization catalyst can be used for copolymerization of ethylene oxide to prepare
antistatic additives of this invention. Epoxide polymerization catalysts known in the art are anionic catalyst,
catalysts based on metal oxides, alkoxides, or carbonates, and coordination catalysts based on an
organometallic compound. Among them, coordination catalysts are preferable. Exemplary of coordination
is catalysts based on an organoaluminum compound which has been modified with water or alcohol or diols,
and/or a chelating agent have been described in U.S. Patents 3,135,705; 3,135,706; 3,219,591; 3,280,045;
3,058,923; 3,642,667; and 4,460,703; and German Patent 1,109,901.
Exemplary of coordination catalysts based on an organoaluminum compound and a metal salt of a beta-
diketone have been described in U.S. Patents 3,396,125; 3,457,197; 3,468,860; 3,484,388; 3,506, 597; and
20 3,925,317.
Exemplary of coordination catalysts based on an organoaluminum compound which has been modified
with a phosphoric acid have been described in U.S. Patent 3,770,664 and Japanese Patent 50-124,999.
Exemplary of coordination catalysts based on an organomagnesium compound have been described in
U.S. Patents 3,766,901; 3,770,655; and 3,450,603.
25 Exemplary of coordination catalysts based on u.-oxo-bismetallic trinuclear alkoxides have been de-
scribed in U.S. Patents 3,432,445; and 3,657,149.
Exemplary anionic catalysts are potassium hydroxide and sodium hydroxide described in U.S. Patents
2,923,690 and 1,976,678; and German Patent 616,428; and British Patent 346,550.
Exemplary catalysts based on metal oxides, alkoxides, and(or) carbonates have been described in U.S.
30 Patents 2,866,761 and 3,441 ,521 ; and British Patents 793,065 and 799,955.
Copolymerization of the ethylene oxide is carried out using a coordination catalyst system and
anhydrous conditions under nitrogen, preferably in an inert diluent. The process may be conducted as a
batch or continuous process with a catalyst, monomers, and the inert diluent added simultaneously or in
increments during the polymerization, or continuously throughout the polymerization. Ethylene oxide and
35 one or more comonomers are preferably added to the reactor simultaneously or as a mixture, or premixed
with the inert diluent before adding the mixture to the reactor, resulting in random copolymers.
Any diluent that is inert under the polymerization conditions can be used, such as for example: toluene;
benzene; heptane; hexane; butane; cyclohexane; diethyl ether; chlorobenzene; methylenechloride; and
ethylenedichloride. Obviously, any mixture of such diluents can be used and in many case preferable.
40 Depending upon the solubility of the copolymer formed in the diluent, the process could be solution
polymerization or slurry polymerization.
The polymerization process can be carried out over a wide range of temperatures and pressures.
Usually it will be carried out in a temperature range of -50 ° C to 200 ° C, and preferably within the range of
from -30 °C to 150°C, and most preferably from 60 °C to 120°C. The copolymerization temperature can be
45 controlled by jacket cooling/heating or reflux, or both. Usually the copolymerization process will be carried
out at superatmospheric pressure up to several hundred pounds per square inch, or, on the other hand, at
subatmospheric or autogenous pressure. The pressure selected depends upon the comonomer selected
and is well within the skill of the art to choose the applicable pressure and temperature.
The ethylene oxide copolymer antistatic agent is functional with a wide range of plastics which require
50 the antistatic agent. The antistatic polymeric composition of this invention comprises at least one antistatic
additive of ethylene oxide copolymer in the range of from 3 to 30% by weight and a polymeric material in
the range of from 70 to 97% by weight. Standard symbols for polymeric materials are described in ASTM
D4000 and are adopted herein. For example, the polymeric materials may be copolymers of styrene and/or
a-methyl styrene and acrylonitrile such as copolymers of styrene and acrylonitrile (SAN), terpolymers of
55 styrene, acrylonitrile and diene rubber (ABS); copolymers of styrene and acrylonitrile modified with acrylate
elastomers (ASA); and copolymers of styrene and acrylonitrile modified with ethylene propylene diene
monomer (EPDM) rubber (ASE). Polystyrene and high impact polystyrene may also be employed. Other
polymeric materials include polycarbonate (PC), thermoplastic polyesters (TPES), including polybutylene

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 EP 0 287 092 B1

terephthalate (PBT), polyethylene terephthalate (PET), and polyether-ester block copolymers (PETG), such
as Hytrel® by DuPont Corp.; polyurethane (PUR); and termoplastic polyurethane (TPUR); polyphenylene
oxide (POP); polyacetals (POM); copolymer of styrene and maleic anhydride (SMA) and polymethyl
methacrylate (PMMA); and mixtures thereof.
5 For the purpose and scope of this specification, the term of "polymeric material," which the antistatic
additive of this invention incorporated, is expanded to include its closely analogous polymers and its
derivatives, and its copolymers. These compositions include but are not limited to comonomers of vinyl
alkanoates such as vinyl acetate and the like, vinylidene halides such as vinylidene chloride, alkyl esters of
carboxylic acids such acrylic acid, ethylacrylate, 2-ethylhexyl acrylate, and the like, unsaturated hydrocar-
io bons such as ethylene, propylene, isobutylene, and the like, allyl compounds, such as allyl acetate, and the
like. Also for example, the term "terpolymers of styrene, acrylonitrile and butadiene (ABS)" originally
denoted a polymer primarily constructed from acrylonitrile, butadiene and styrene, this definition has been
expanded to include polymer resins in which these components have been replaced in whole or in part by
similar analogue compounds. Exemplary of analogous compounds of acrylonitrile are methacrylonitrile,
is ethacrylonitrile, halogenated acrylonitriles, and the like; exemplary of analogous compounds of styrene are
alpha-methyl styrene, chlorostyrene, vinyl toluene and the like; exemplary of analogous compounds of
butadiene is isoprene, and the like.
The ethylene oxide copolymers of this invention are also ideal antistatic additives for polymer blends
which are the physical combination of two or more polymeric resin systems where at least two of the
20 polymers are present in concentrations greater than 5%. The principal reason for blending is to improve the
product cost and/or specific property and process performance of a polymer for a specific end-use
application. Exemplary polymer blends are ABS/PVC known commercially as Cycovin® by Borg-Warner,
Lustran® by Monsanto, and Polyman® by A. Schulman Inc.; ABS/PC known commercially as Bayblend® by
Mobay and Proloy® by Borg-Warner; ABS/nylon commercially known as Elemid® by Borg-Warner;
25 ABS/SMA known as Cadon® by Monsanto; PVC/ASA known as Geloy® by General Electric; PVC/acrylic
known as DKE® by Sumitomo and Kydex® by Rohm & Haas; PVC/urethane known as Vythene® by Alpha
Chem & Plastics; PVC/CPE called Hostalite® by American Hoechst; PVC/nitrile rubber called Vynite® by
Alpha Chem & Plastics, Hycar® by BFGoodrich, and Paracril® by Uniroyal; Acetal/elastomer commercially
known as Celcon® by Celanese, Duraloy® by Celanese, Delrin® by DuPont, and Ultraform® by BASF;
30 PBT/PET known as Celanex® by Celanese and Valox® by General Electric; PBT/elastomer called Duralox®,
Gafite® and Gaftuf® by Celanese, Valox® by General Electric, Ultradur® by BASF; PET/PMMA called
Ropet® by Rohm & Haas; PC/PBT/elastomer known as Xenoy® and Valox® by General Electric; PC/PE
known as Lexan® by General Electric and Merlon® by Mobay; PC/PET known as Xenoy® by General
Electric and Makroblend® by Mobay; PC/SMA known as Arloy® by Arco Chemical; PC/TPU known as
35 Texin® by Mobay; POP/high impact PS known as Noryl® by General Electric and Prevex® by Borg-Warner;
POP/polyamide known as Noryl® by General Electric; SMA/high impact PS called Dylark® by Arco
Chemical; Nylon/elastomer called Ultramid® by BASF; Nylon/ethylene copolymer called Capron® by Allied
Chemical, Nycoa® by Nylon Corp. of America, Grilon® by Emser Industries; Nylon/EPDM commercially
known as Zytel® by DuPont; Nylon/PE known as Selar® by DuPont.
40 Any plastic in need of an antistatic agent can be employed along with the copolymers of the ethylene
oxides of the present invention. However, the antistatic properties are more effective with certain plastics
and thus the properties are not uniform between polymeric materials when a constant amount is employed.
Additionally, the composition of the ethylene oxide comonomer also effects the antistatic properties.
The composition of antistatic polymeric materials of the present invention can be prepared by
45 mechanical mixing under the influence of heat and/or pressure by a variety of methods. The actual method
chosen will depend to some extent on the nature of the polymeric materials and on the desired final
physical form of antistatic polymeric materials. Antistatic additives of this invention can be incorporated into
polymeric materials together with other compounding ingredients, such as lubricants, plasticizer, stabilizer,
fillers, impact modifier, and processing aid, or incorporated separately before or after the polymeric
50 materials are compounded. Once the antistatic agent is compounded with the polymeric material, the
antistatic agent tends to migrate to the surface so that it tends to concentrate there and is less concentrated
further removed one is from the surface. A well-dispersed composition (despite the migration) is especially
preferred because moldability and antistatic properties are especially enhanced and physical properties are
less impaired. An ordinary mixer, roll mill, or calender, may be used to incorporate antistatic additives of
55 this invention into polymeric materials to form entirely satisfactory blends at convenient and customary
operating conditions. For example, antistatic additives of this invention can conveniently be incorporated into
a polymeric material by a biaxial extruder and molded or extruded directly into a final product, or it can be
extruded in the form of rods which are chopped up into pellets and used in subsequent operations. Another

8
 EP 0 287 092 B1

example is to use a Banbury mixer to give a moldable composition, then the composition is rolled by a mill
to form a thick sheet and cubic pellets of the composition are obtained subsequently using a screen
granulator. Final articles of antistatic materials can be formed by compression molding, injection molding,
blow molding, extrusion, or calendering.
5
EXAMPLES

The following examples are given to further illustrate the present invention. The antistatic properties of
polymers were determined by surface resistivity and static decay time. Both measurements were carried
io out under controlled conditions at 25 ° C with 50% relative humidity. The samples were also conditioned at
least 48 hours prior to measurement.
Surface resistivity testing is conducted in accordance with ASTM D257 with an Electrometer (model
617) equipped with a high voltage supply (model 247) and a resistivity adapter (model 6105) all from
Keithley Instruments, Inc. The adapter comprises an upper circular electrode and a lower circular electrode
is encircled with a ringing electrode. A sheet sample 8.89 cm (3.5 inches) in diameter and 3.23 - 1.61 mm (1/8
- 1/16 inch) thick) was placed between the upper and lower electrodes and a voltage of 500 volts was
applied between the electrodes. After 60 seconds, the current was recorded from the Electrometer and
converted into surface resistivity in ohms per square using the equation derived from the dimensions of the
electrodes.
20 The end use of the polymeric antistatic material will determine the desired antistatic properties. For
example, sophisticated electronic equipment would require a higher degree to antistatic properties than
carpet or articles of clothing. Accordingly, different standards have been developed for specific end use
applications. For example, electrostatic behavior has been characterized by the Department of Defense in
publication DOD-HDBK-263 in terms of surface resistivity. Materials with a surface resistivity in the range of
25 109-10H ohms per square are antistatic. Materials with a surface resistivity greater than 10H are insulators.
An effective internal antistat will provide surface resistivity in the area labeled antistatic in the above
governmental document. When measuring surface resistivity in the following examples, the Department of
Defense Standard was used.
Different standards have also been developed for the static decay test. The static decay test is carried
30 out according to Federal Test Method Standard 101B, Method 4046 with a Static Decay Meter, model 406C
obtained from Electro-Tech Systems, Inc. Static decay is a measure of the ability of a material, when
grounded, to dissipate a known charge that has been induced on the surface of the material. A sheet
sample 7.6 cm x 15.2 cm (3" x 6") with 3.36 - 1.61 mm (1/8-1/16 inch) thickness is placed between clamp
electrodes contained in a Faraday cage. A 5,000 volt charge is applied to the surface of the specimen and
35 the time in seconds required to dissipate the charge to 500 volts (10% of its initial value), after a ground is
provided, is then measured. Highly insulative materials will not accept a full charge of 5,000 volts on their
surface or show residual charge before applying a charge. In both instances, a static decay test cannot
apply and the materials are indicated in examples as being insulators. The National Fire Protection
Association in NFPA, code 56A, "The Standard for the Use Inhalation Anesthetics" covers products used in
40 the hospital operating room and in hazardous environments. It requires that the applied charge drop to 10%
of it initial value within 0.5 seconds at 50% relative humidity in order to qualify for use in hospital operating
rooms and other hazardous environments. When measuring static decay in the following examples, the
above standard was employed as the desired goal.
Generally, a more conductive material with lower surface resistivity will show better antistatic properties.
45 However, many cases have been found where static behavior is not always related to the surface resistivity
of the materials. One of the main reasons is believed that static dissipation is not only by conduction, but
also by discharge static electricity into the air. Consequently, materials having same surface resistivity
might have different decay rate.
The following physical tests used in Example 8, for example, are carried out in accordance with ASTM
50 standards: Tensile, ASTM D-638; Flexural, ASTM D-790; Heat Distortion, ASTM D-648; Izod Impact, ASTM
D-256; and Durometer Hardness "D", ASTM D-2240.
In all examples, antistats of ethylene oxide copolymers and comparative commercial antistats are mixed
with thermoplastics or thermoplastic elastomers in a Brabender mixer heated with hot oil. After mixing is
completed, a 15.24 cm x 15.24 cm x 0.32 cm (6" x 6" x 1/8") or a 15.24 cm x 20.32 cm x 0.16 cm (6" x 8"
55 x 1/16") sheet sample was press-molded. Samples were visually examined for detrimental effects of
antistats such as marblizing or oiliness on the surface, discoloration or decomposition of polymers and
brittleness.

9
 EP 0 287 092 B1

EXAMPLE 1

Antistatic ethylene oxide copolymers were synthesized in one quart, conditioned beverage bottles and
capped with self sealing rubber gaskets and two-holed metal caps under nitrogen. Sieve-dried toluene,
5 ethylene oxide, and comonomer were added sequentially. Polymerization was initiated by adding the
catalyst and proceeded by tumbling in an oil bath at 110°C. At the end of polymerization, a sample was
withdrawn to measure total solids for percent conversion and the polymerization were short-stopped with 8
ml of isopropanol containing hindered phenolic antioxidant at 0.3 weight percent to the theoretically
calculated expected polymer. Then heptane was added to precipitate the polymer and copolymers were
io dried at 60 °C under vacuum overnight. In order to obtain sufficient amounts of copolymers, copolymers
obtained from several duplicated bottle polymerizations were combined. In all polymerizations, coordination
catalyst solutions prepared according to U.S. Patent 3,219,591 were used. The molar ratio of catalyst
ingredients of triethylaluminum, anhydrous tetrahydrofuran, water, 2,4-pentanedione are 1:2:0.6:0.15-0.60.
For comparison, high molecular weight ethylene oxide homopolymers were also synthesized.
is Conditions of preparation and characterization of the ethylene oxide copolymers are set forth in Table I.
Copolymers of ethylene oxide with ethylene oxide in the range from 32 to 93 weight percent were prepared.
The following symbols are used for comonomers:
PO = propylene oxide
DO = dodecylene oxide
20 BGE = n-butyl glycidyl ether
EHGE = 2-ethyl hexyl glycidyl ether
Most copolymers were obtained in good yields greater than 80% conversion within three hours
polymerization.

10
 EP 0 287 092 B1

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Dilution solution viscosity (DSV) was measured at 0.25 grams per 100 grams toluene at 25 °C with
55 capillary viscometers according to ASTM D2857 referred to therein as inherent viscosity. Molecular weight
of copolymers determined by gel permeation chromatography (GPC) using a Waters GPC Model 200
instrument at 40 °C in tetrahydrofuran. Molecular weights were calibrated with respect to standard poly-
styrenes. Because of broad molecular weight distribution, the interpretation of actual molecular weight of

11
 EP 0 287 092 B1

copolymers by GCP is difficult. The weight percent of the ethylene oxide in the ethylene oxide copolymer
was determined by proton Nuclear Magnetic Resonance (NMR) at 60 megahertz (MHz) using a Varian T60
NMR Spectrometer. The glass transition temperatures (Tg) and melting points (Tm) were measured by
Perkin Elmer DSC-2 differential scanning calorimeter at 10 °C per minute heating and cooling rates from
5 -120 ° C to 100 ° C under 20cm3 per minute of helium purge. Thermogravimetric analysis was conducted on
a DuPont 951 thermogravimetric analyzer at 10 °C per minute heating rate from 30 °C to 825 °C under a
180cm3 per minute nitrogen purge. Copolymers of ethylene oxide/propylene oxide with ethylene oxide in
the range from 32 to 70 weight percent are elastomeric, from 70 to 90 weight percent are semiplastic, and
from 90 weight percent and above are plastic. All antistats of the ethylene oxide comonomers are thermally
io stable and able to sustain the process temperature of most plastics. This experiment demonstrates that a
variety of comonomers can be employed with EO to make an antistatic agent within the correct molecular
weight or DSV for the present invention.

EXAMPLE 2
15
In this example the antistatic ethylene oxide copolymers of Example 1 were incorporated into a
semirigid PVC injection molding compound to determine the antistatic properties of the antistatic agents.
The PVC compound is composed of:

20
Geon® PVC homopolymer resin (registered trademark of B.F. Goodrich Company) 100 weight parts
Impact modifier 12 weight parts
Processing Aid 2 weight parts
Stabilizer 2 weight parts
Stearic Acid 0.5 weight parts
2i.

The mixing was conducted at 170°C in a Brabender mixer. The results of the antistatic properties of
100 parts of PVC compound containing 10 parts of antistatic ethylene oxide copolymers are set forth in
Table II as examples 2B-2K. Example 2A was the control containing no antistatic agent but merely the
30 semirigid PVC injection molding compound. All PVC compounds having 10 weight parts of the antistatic
agent had surface resisitivities less than 10H ohm/sq. without any detrimental effect being visually observed
upon examination. It was found that copolymers of ethylene oxide and propylene oxide are more effective
antistatic additives than copolymers of ethylene oxide with other comonomers of 1,2-epoxide. It was also
surprising to find that the anti static properties of the PVC compound are rather insensitive to the
35 composition of ethylene oxide/propylene oxide antistat in the range from 32 to 85 weight percent EO.

40

45

50

55

12
 EP 0 287 092 B1

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EXAMPLE 3

For the purposes of comparison, an ethylene oxide homopolymer, low molecular weight liquid ethylene
oxide/propylene oxide random copolymer, and low molecular weight ethylene oxide/propylene oxide block
55 copolymers were examined with the PVC compound used in Example 2. An ethylene oxide homopolymer of
Antistat K made in Example I was synthesized in the same manner as the ethylene oxide/propylene oxide
copolymers of this invention. Another ethylene oxide homopolymer (referred to as "commercial") was
obtained from Poly Science, Inc. with an average molecular weight of 5 x 10G. Both ethylene oxide

13
 EP 0 287 092 B1

homopolymers are uneffective antistats, i.e. both are classified as insulators according to the Department of
Defense standards mentioned previously. Another commercially available antistat which was compared was
Carbowax® 4000. Carbowax® 4000 is a low molecular weight polyethylene glycol obtained from Union
Carbide Company. Using polyethylene glycol as an antistat is well known. However, polyethylene glycol is
5 difficult to blend into the PVC compound and the sample became brittle.
Low molecular weight liquid ethylene oxide/propylene oxide random copolymers were obtained from
Union Carbide under the tradename Ucon® and compared. The amount of ethylene oxide vary from 0 to 75
weight percent. Example 3D has an average molecular weight of 12,000; Example 3E has an average
molecular weight of 2,500; Example 3F has an average molecular weight of 1,050; Example 3G has an
io average molecular weight of 4,000; Example 3H has an average molecular weight of 2,600; and Example 31
has an average molecular weight of 1,220.
Though the Ucon® polymers provide good antistat properties, all samples became brittle and most
showed poor surface properties (blooming, marblizing, and/or oiliness).
Block copolymers of ethylene oxide and propylene oxide were obtained from BASF Wyandotte
is Company under the tradename of Pluronic®. The amount of ethylene oxide can vary from 10 to 80 weight
percent of the antistat. This amount is indicated as the number before the word Pluronic in Table III.
Example 3J had an average molecular weight of 3,250; Example 3K has an average molecular weight of
4,000; Sample 3L had an average molecular weight of 3,250; Sample 3M had an average molecular weight
of 4,000; and Sample 3N had an average molecular weight of 4,000. Most Pluronic polymers provide
20 antistat properties. However, they were difficult to blend with PVC and it is theorized that the same problem
would occur with other plastics such as ABS, etc.. All samples became brittle and most showed poor
surface properties such as those mentioned above with respect to the liquid copolymers. The results of
these samples are set forth in Table III.

25

30

35

40

45

50

55

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55 EXAMPLE 4

For the purpose of comparison, commercial non-ionic antistats were examined with PVC compound
used in Example II. These antistatic agents were obtained from Argus Chemical Division of Witco Chemical
 EP 0 287 092 B1

Company under the trade name of Markstat®. These commercial antistats are for rigid or plasticized PVC.
The antistatic agent used in Sample 4A is a alkyl ethoxylated blend; the antistatic agent used in 4B is the
same as that used in 4A except that the percent weight of antistatic agent is significantly lower; the
antistatic agent set forth in samples 4C and 4D are polyether blends. The results are set forth in Table IV.

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55
Samples 4A through 4C all show poor antistatic properties. Although sample 4D showed good antistatic
properties, but the sample was brittle and showed poor surface properties (blooming, etc.) such as those
mentioned previously. In the prior art section of this disclosure, it was stated that anionic and cationic

16
 EP 0 287 092 B1

antistatic agents cause poor surface and physical properties when blended with polymeric materials.
Additionally, it was pointed out that the anti static agents of the present invention are nonionic. Example 4
demonstrates that some nonionic antistatic agents can also cause poor surface and physical properties.
Accordingly, the present invention is more than merely employing a solid nonionic antistat.
5
EXAMPLE 5

For comparison purposes, commercial cationic antistats based upon amines, amides, and phosphates
were examined with the PVC compound used in Example II. The amines were ethoxylated and obtained
io from Humco Chemical Division of Witco Chemical Corp. under the trade name of Kemamine®. These
antistats of ethoxylated amines are well known for use with polyolefins and also available as Armostat® from
Noury and Markstat® AL-10 from Argus. Ethoxylated amides were obtained from Akzo Chemie America
under the trade name of Ethmid® and from Onyxol Chemical Company under the trade name of Onyxol®.
Phosphate ester was obtained from Emery Industries under the trade name of Tryfac®. Phosphate esters
is are also available as Gafac® from GAF Corporation and Zelec® from DuPont. Phosphate esters are well
known antistats for textile applications. The percent weight of ethylene oxide in the antistatic agents are set
forth in Table V. While some antistatic additives show good antistatic properties, all samples discolored
which indicated the decomposition of the PVC compound. Cationic antistatic agents generally cause
stability problems of PVC compounds. The non-ionic antistats agents of the present invention are superior
20 to cationic antistatic agents since non-ionic antistats cause no stability problems.

25

30

35

40

45

50

55

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O Q X i-3 SMO CJ >
\^ \^ \^ —«
CJ U CJ CJ CJ CO to 3
3
D
H
3
3
J -U > -i
d 3 i 3.
s u a 1 U
4) JHBHHOO J
• 3 *3 9 * * 0
eo 3 ca o oj eg o o H
j .h d d d d
rH rH rH -I
3
o

r-l -n rH NO© w ''

a > o 4/ rH rnH \r> © rH
a
n •* to - + + + rH + + +
1H H H + M W H a
u co a >O O O M O O O
3-h£ 5 O m CMO •» O CN4
/3 COO CM
4) 1 rH NO CMrH CO vO
at

O
a* W ^p* '
3 in m m m rH
©m n
4) 31 "■H
H
O
<e «
H

T T W
r» r» on o
On On On H
I I I cn O
CO C/J CO CMNO
hj •< •< >v in m
@oj@oj®oj Is as cn■) cn
o a a -h fi o o
1 1 1 Ji ii g. g.
4} 53 4) 4J 4J c d
MM MMO O

II
cm cm cm >o eo cn cn oa

v
d d : a a b Tj
-4 I •H H <H H H

4)
a
«H
m m in m m m m
*

EXAMPLE 6

For comparison purposes, commercial cationic antistats of quaternary ammonium salts were examined
with the PVC compound used in Example 2. Quaternary ammonium salts were obtained from Argas

10
 EP 0 287 092 B1

Chemical Division of Wico Chemical Company under the trade name of Markstat® and from American
Cyanamide Company under the trade name of Cyastat® as heat stable antistats. The results are set forth in
Table VI. All the samples had low surface resisitivities with the exception of Sample 6c, which decomposed
and discolored so badly that no surface resistivity measurement could be made. All of the samples
5 discolored to an unacceptable level.

§
10 rH
» t» rQ
o o o o O
I-l
ft u o»
cu cu V «r< V (I
CJ
UH •J J rH 1-3 rJ «
4J Q3 ^ w
15 cu U U ^ U U (H
a 3
CO
II
cu »«n
4-1 4J co
« 3
OS u o •a
co v U1 CO • rH 00
20 H >>K W C) r- C © rH
J « o
< OH fl © rH o o
CO 01 >-» «»H
a co
§
rH
rQ
4J o
25 (14 CJ -H • CMCM On rH I-l
0 o >■ a rH rH O rH a.
rH CO"H CO + + + +
> CO, lM 4J S WW - W W >>
H M CO e © © T3 O © 4J
cu < 3 h i <f fl • rH CJN
rH (H CO CDO • • fl • •
X! tO 41 CM00 rH ID
CO rH CM rO
H H CO
30
4J
J «
< trt 4J in in ia in m u
rH 03 o
rj »iH f> CMCO CO CO rH
OCt 4-1 4J o
1 * 3 u
35 II
u
CO CO CM
CO CO rH
I I I O)
S rH
c 3 4->
cu 2 f l a . J *
40 1 •3 cflfl «a~4J~4J
cS C I*
o 4J 4J 4J 03 CO
u CO CO CO 4J 4J
M M M co a II
U U U 9 «
« « a >< >< S3
rc s c u u
4J
45 CJ
4)
a
4-> H
CO 03 (0 < «
3 3 3 3 3
©* ©* o* o* o*
fl
50 0)
4) a
rH
*j a U Q H
^n ^3 ^3 ^3 0)
x Q
H «
55

19
 EP 0 287 092 B1

EXAMPLE 7

In this example, antistatic EO copolymers of this invention were examined for ABS thermoplastics. ABS
thermoplastics are terpolymers of acrylonitrile-butadiene-styrene. The following ABS thermoplastics ob-
5 tained from Borg-Warner Chemicals were studied:
1. Cycolac ®T, a general purpose molding material, mixed at 190°C.
2. Cycolac ®L, a high impact injection molding material, mixed at 190°C.
3. Cycolac ®KJB, a medium-impact, flame-retardant injection molding material, mixed at 185 °C.
4. Blendex® 131, a material for calendered sheet applications and a modifier for PVC products, mixed at
io 180 °C.
As shown in Table VI, EO copolymers of this invention were effective antistats for ABS thermoplastics.
On the other hand, EO homopolymer, low molecular weight EO copolymer, and amine type antistats were
uneffective. Table Via shows the physical properties of Cycolac® L and T ABS thermoplastics containing
EO copolymers of this invention. The results indicate that the antistatic agents of the present invention are
is useful with ABS polymeric materials.

20
 I . . . . + ♦ I + +
I I I I I HH I H H
rH O U-l \0
• • • •

n m <■
H H H
0 + +
■3 1 I M H
M I I I I I
© I CO I I CO rH CO CMl
M I I *O rH
H I I I I I
• • • • • • • •
rH <f rH IT) CO rH
A

1 n n
+• H - H - H - H - H - H . ' ^ lH rH
4k- l+!
rH
+
4 M M I I I I I I I
t rH to I I I I I I I
• • •
H rH rH

rH
I I I I I I I W I I
I I I I I I I © I I
rH

5 lO © O O O O O lO lO
H rH CMrH rH H H H

CO
H © © | | |
> «m cn < © eo i i i
9 CO OK H rH
to
HH

rH
rH r»
U CO cM
M O I O
M rH CO rH
3 M S3 £ rH bu «C <T
• mm u o «-« e eg
4 ii u u c "H *•>
B CB OB Q VOS.i CO
H H H K I h O
s q c oh « c
t < < C4 Oft.* •<
HH
U e5
> O U •< O cj cu
M CU CO 0* Oa C C
» oo o o o a a
a MM U MM< <
 fcP U 287 092 Bl

52
s i r
*5
•4
r3
V9,
«0J
«J I* •J
u

3 |

S3* o
E *a■>o* _>n
3 v.
sr
■3-r?
i « S
3 1
5*
i
6
-3
3 S ■s.—«• — •
t
S5i
e
9
- a*
** »©
n M re» XX
V
S) e si
u
EI-
»—
I
-- - 5

«■ **■ i i 1 v«

* *I
i ►
-»'—
" a
1•;' sW s
la m

*. <H
w(9>I■
;| S ° • > * H>
"J, :
i m
fc>• o
N —*
i 5 % a

:/\rtivir Liz o

In this example, antistatic EO copolymers of this invention were examined as antistats for polystyrene,
ighty parts high impact injection molding polystyrene, commercially known as Cosden® 945, was obtained
 EP 0 287 092 B1

from Cosden Oil and Chemical Co. and mixed with 20 parts of Antistat C at 190°C. The mixture gave a
surface resistivity of 5.3x1 012 ohm/sq. and a decay rate (10% cut) of 0.75 sec. Cosden 945 without antistat
gives a surface resistivity of greater than 1015 ohm/sq. and is an insulator as indicated by the decay rate.
Eighty parts of Styron® 420, obtained from Dow Chemical Co., was mixed with 20 parts of Antistat C at
5 190 °C. The mixture gave a surface resistivity of 9.6 x 1011 ohm/sq. and a decay rate (10% cut) of 0.6 sec.
Styron 420 without antistat gives a surface resistivity of greater than 1015 ohm/sq. and is an insulator as
indicated by the decay rate. The results are summarized in Table VII.

EXAMPLE 9
10
In this example, antistatic EO copolymers of this invention were examined for impact-modified styrene-
maleic anhydride terpolymers, a polymer blend of ABS and styrene-maleic anhydrin copolymer (SMA). To
90 parts of high heat grade ABS/SMA polymer blend, commercially known as Cadon® 127, obtained from
Monsanto, was mixed with 10 parts of antistat at 190°C. Antistat A gives a surface resistivity of 3.8 x 1012
is ohm/sq. and a decary rate (10% cut) of 1.2 sec; Antistat D gives a surface resistivity of 4.5 x 1012 ohm/sq,
and a decay rate (10% cut) of 1.2 sec. Cadon® 127 without antistat gives a surface resistivity of greater
than 1015 ohm/sq. and is an

20

25

30

35

40

45

50

55

23
 CO • • •
<N rH CM

«j ©
** rH O m •X rj
OB + © —
*rH* r-^
a. -h r* o u • w <m <• < O
swr^rH rH r-~ <■ • CO • •
O C rH cn- lO
V '° cm cn co
m
W Hj CM
I
O 3! rM
>
O rH « S > ISl *M
M + rH ^ _
*-> ii h p <r W to CO ~2 r-s
vO
C I I o a co • CO •
o • c 'CO vO rH
<-( f» *^/
cn
O rH rH — — OC
cn
rt-
r J*•o
CM
O I rH ITl •
CX, I fx o H- r-» TJ •a o ©
\ u oj cn • . . • • •
o o c c < H1 N
^

o w + © £ ^
fiNO h <r ^cn <r• <• O © CM
s < r» rH cn • « • •
o l • o m cn CM CMCM
w i co G«w
u
o _ ,j, 00 v*
rH m *j
t» r-
it m *^ cm v rr-»
>» cn
n cn ' P
C I I o a o • • •
O C cm CM fSJ CM
O rH HH

O X
■T S rH X
I 1 -H
o <o > ea
_JC C U> Q" o
CM N ~ O
H £*" IV. «O
cn •£ Q r-<a CO ^ -
■< cn « O
-r"^ H I U rH
C -H W f^O■ Q J3 X
o a < «h
-r-i a. ^ c u a
u - c h « a'
u <■ U ft to —
O «9 US •< X -
Uw CM « • 4J 01
a a rQ « to p
H W 8 rH V C rH
Q « rH rH CJ 3
H MT)
J-J U TJ *-> C3 i-> O
« • O «h CJ to SC
V N '— CJ
K rH H
 EP 0 287 092 B1

Table VIII

<inH.t.tle «nd P h v i e a l P r o p e r t i e s of S v t r e n c - Majelc

Anhydride T e r p o l v m e r

Example Wo. HA

Antistat Control EO/PO EO/PO

ID Antistat A Antistat B
EOX 85 60
wtX 0 10 10

Surface Resistivity, ohm/aq >1.0Z+15 3.8E+12 4.5E+12

rate at 10%, aec. Insulator 1.20 1.20

Decay

F l e x u r a l Tests/ASTM D-790
Modulus, tpsixlOOO) MPo. (352) 2V2S" (267; i S i 9 (269) 18S3
S t r e n g t h , (psixlOOO) (8.2)^-4.5 (5.8)37.9 (5.6>3f.6

Heat D i s t o r t i o n , ASTM D-648

•C at (264 pai) O.M HP* 98 103 98

Izod Impact, ASTM D-256

( f t - l b / i n of n o t c h ) MSS^/iSm* 3.6 5.1 2.2

Tensile/ASTM D-638
S t r e n g t h at y i e l d , (1000xpsi)rcfe (4.2)2,?.? n.d. (2.3)*S.fJ
Modulus, (100, OOOxpsi) 1,000 t\f* (3.2)i.2 n.d. (2.3) i . s t

Durometer H a r d n e s s "D"
ASTM D2240 80 73 73

insulator by decay rate. Antistatic and physical properties of Cadon® 127 are shown in Table VIII.

EXAMPLE 10

In this example, antistatic EO copolymers of this invention were examined as antistats for polyacetal.
Celcon® M270-04, obtained from Celanese Co., is a high flow injection molding grade polyacetal. It was
mixed with antistats at 195°C. As shown in Table IX, Antistats B, D, E and J (see Example 1) of this
invention are effective antistats for polyacetal (Example 10B-10I). On the other hand, polyacetal containing 5
parts of Kemamine® AS-974/1 (see Example 5) shows no improvement on surface resistivity or static decay
rate (Example 10J).

25
 P 0 287 092 Bl

k 2 io

«n t
'2

« C4 > » «" ©
3 n• n ^
—

> «0 O
O

■4
91s nN O
n O

1 2 a te o«o<•> 3
3 e
J ft*
a 3
£oo
S" X H
a * IS 9 INI/1
—w N

S NO
o • <•»
m"s

3-
5 I n• sP4 r. <e o
oM

ew r> O O
■e ueo

1
o
~8.
Si •5 fl g
7 S * •O
XM
e ■ 3?
P«4mo,■—O *
v•<> 49 —-■
u
•93? a m
■ ->
- t. « M C
8i 1- V
<I
5 5 5

EXAMPLE 11

In this example, antistatic EO copolymers of this invention were examined as antistats for modified
polyphenylene oxide. Noryl® PC180, a polymer blend of polyphenylene oxide and polystyrene obtained
 EP 0 287 092 B1

from General Electric Co., is a computer and business equipment grade of polymeric material. It was mixed
with antistats at 180°C. As shown in Table XI, Antistats B, C and E of this invention are effective for
modified polyphenylene oxide.

CX Oo
CM f-1 «•
rH £ 5»
+ CO ^I f l_^ CO
Cm CMO M rH ? m o
WS H N • to • fl e
O • O rH CM
--> h rH
«
xi
a
™h
V + o J~ ^ •M
•O fl 2 CMO M CM CMC ON
ON
CO er> cn
tH rH • CM • • •
X O • <t COwvO
o H m —
cj
cAt rH
rH • •
+ <• 13 •O
0. s o H o . . •a t3
1 u \ r- cm rH . c e (3 fl • •
o • © fl fl C
x> H
Q •J
CM £ 3
2 «?
o o < H « m
CM rH • • • •
4M cn Is*
V>r
o
m» ~
> >*
O cn T- «s|
JC CX. CMO o CMSo" CI
O '-f
HH r^
CO V. CO (M rH • • CM
>*H o cm cn • • vO
o w -- rH N CM
•9
GO — 9-
CO y
nCMJ" in .
a 0h CMo o <-> S~* in ^ ^
v ^ S CO H rH SO SO CO rH Cn
O. o CM • CO • • •
o cn <e rH CO CM
O M CM
Xi
o o-
u o rH « rj "0 Si r4
-rH H X. H- O
CO C *J H 9 rH CM o vO
> o c O a o . CO • • • CO
SE O e cn e* -H jn
ft- U
•O
c c
z
3
X. P
a o «r u
ON c W
2 • ' c! r I iH »-
o u Q r Q «o B
m a
«
4)
a
_ „«
5^ CMJ3 w oo
P o o I (J -o
u « CO O rH CO«o a aj SO M -
*H K •< O •< 1 o m « o B
> o 15 fl B
o 1 Xl rH 0)
r-l rH CO *M 3 rO M c
a -rH G3 o a •< o tH •o
a 4-> u naa0, ■H Qa E xi a xi o
•H « a —- 4-1 - c h <o a «B <T
a co • x< <r U -rH O w J3 CM
CO 0) H « J3 o vO CJ ^ < rfl - CM
sc a xi xi C M a • *J B X. |
k4 « •H S 00 a — O. rO cj a
v B V u « rH C? -H AJ S -H CO" fl rH
rH u X< 3 4) a « H CO 3
a. a a, k x cd >, 3 TJ X, H X TJ IfH
H >, O
I *4J M « How *-> u n o o O CO
1 2-J H W X. CJ CJ £ to « o O VM c to r x< <
09 2 9
o a
V V N "— CJ p
X H a

17
 EP 0 287 092 B1

EXAMPLE 12

In this example, antistatic EO copolymers of this invention were examined for polyester. Hytrel® 6346,
obtained from DuPont Co., is a thermoplastic elastomer of a polyester-ether block copolymer comprising
5 polybutylene terephthalate (PBT) hard segments and polytetramethylene glycol terephthalate soft segments.
To Ninety parts of Hytrel® was mixed with 10 parts of Antistat A at 210°C. The mixture gave a surface
resistivity of 9.4 x 1011 ohm/sq. and a decay rate (10% cut) of 0.15 sec. Hytrel® 6346 without antistat gave
a surface resistivity greater than 1015 ohm/sq and was classified as an insulator by decay rate.

w EXAMPLE 13

In this example, antistatic EO copolymer of this invention was examined with polycarbonate (PC).
Lexan® 141; obtained from General Electric Co. is an injection moding resin. Eighty-five parts of Lexan®
141 was mixed with 15 parts of Antistat C at 225 °C. The mixture gives a surface resistivity of 9.4 x 1013
75 ohm/sq. Lexan® 141 without antistat give a surface resistivity of greater than 101G ohm/sq.

EXAMPLE 14

In this example, antistatic EO copolymer of this invention was examined with polyurethane (PUR).
20 Estane® 58130, a thermoplastic polyurethane, was obtained from B.F. Goodrich Co. Ninety parts of
Estane® 58130 was mixed with ten parts of Antistat A (EO/PO copolymer) at 210°C. The mixture gives a
surface resistivity of 5.0x1 012 ohm/sq. When ten parts of Antistat G (EO/DO copolymer) is incorporated, the
mixture gives a surface resistivity of 3.1 x1013 ohm/sq.

25 Example 15

In this example, permanence of antistatic EO/PO copolymers of this invention was examined. Antistatic
properties of several PVC compounds of Example 2 were measured as a function of storage time. The
results are shown in Table XI.
30 In most cases, the surface resistivity does not change drastically as a function of storage time; with
unknown reason, decay rate is improved.

35

40

45

50

55

28
 EP 0 287 092 B1

r—«
4J
3
u
K
O T3
rH V CMCO rH CM VO rH rH
w kl rH ro «0 CMO O O
0 • • • • • • •
• *J O O O o o o o
CJ CO
V
co
c
10 ft rH
« rH rH O ma n n
4) -H H H N m rH o o
4J 4-1 • • •
« -rH O rH rH o o o o
CS C
M
r*
0
u
15 0)
a
o
co
v.
B CMCO CO CM CMrH rH
.C H H H rH rH rH rH
O Tj O O O o © o ©
20 01 rH rH rH rH rH rH rH
. U XXX X X X X
>i > O r-» O <0 © m a> <■
4J 4-1 4-> . . . • • • «
-H -rH tOi CM<0 * n * in h
rH >
-H *H
rQ 4->
X « -H
W CO rH CO CO CM CMCO rH
25 V CO V HI rH rH rH rH rH rH rH
rH 04 «J O O O © © © ©
Xi 0> -H rH rH rH rH rH rH rH
•3 « 0) 4J XXX X X X X
H CS UH rH o <e co © co co
H « C • • • • • • •
O l« H CMCM«0 «T CO CM CM
u u
CO 3
30 co
VW4J
o <s
4-1
X a m
H o o o •© m ©
• 4J rH rH rH N H H N
35
X
4-» < in o m m m m
> in co co co co co
s1
40
u
4-> 0J o o o o
CO o CO Cm 2 c£t CO 0, n Al (U
*v V -C "X X. V.
4J O O O o o o o
5 B WWW a w w w w
45 O o
a a
©
CS rH
4->
CO m
CJ MOM V < < < <
4J 4J
<4H
50 •<

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

29
 EP 0 287 092 B1

aims

An antistatic polymeric composition consisting of:

a) at least one antistatic additive of an ethylene oxide copolymer in the range of from 3 to 30% by
weight, said antistatic ethylene oxide copolymer being a nonionic solid material at room temperature
having a dilution solution viscosity of greater than 0.25 g/ml
as determined on a solution made up with 0.25 grams of the polymer in 100 grams of toluene
with capillary viscometer at 25 °C according to ASTM D2857, said copolymer excluding epi-
halohydrin; and
b) a polymeric material selected from copolymers of styrene and acrylonitrile; terpolymers of
styrene, acrylonitrile, and diene rubber; copolymers of styrene and acrylonitrile modified with
acrylate elastomers; copolymers of styrene and acrylonitrile modified with ethylene propylene diene
monomer rubber; polystyrene and rubber modified impact polystyrene; polycarbonates; thermoplas-
tic polyesters including polybutylene terephthalate, polyethylene terephthalate and polyether-ester
block copolymers; polyurethane; thermoplastic polyurethane; polyphenylene oxide; polyacetals;
polymethyl methacrylate; and mixtures thereof and their polymer blends in the range of from 70 to
97% by weight, wherein said ethylene oxide copolymer comprises:
a) ethylene oxide in the range of from 5 to 95% by weight; and
b) at least one cyclic comonomer selected from an alkylene oxide containing up to 25 carbon atoms
represented by the formula:

wherein, Ri , R2, R3, and R+ are selected from hydrogen, saturated aliphatic, cycloaliphatic,
monoolefinic aliphatic and cycloaliphatic, diolefinic (conjugated and non-conjugated) aliphatic and
cycloaliphatic, aromatic, and aralkyl, alkaryl; and at least of R1 , R2, R3, and R+ is not hydrogen; said
cyclic comonomer is in the range of from 95 to 5% by weight of the total weight of said ethylene
oxide copolymer;
said ethylene oxide copolymer having a weight average molecular weight from 20,000 to
5,000,000.

The composition of claim 1 wherein said ethylene oxide copolymer is a solid material at room
temperature and has an inherent viscosity in the range from 0.25 to 15.0.

The composition of claim 1, wherein said alkylene oxide is selected from propylene oxide; 1,2-butylene
oxide; 1,2-dodecylene oxide; n-butyl glycidyl ether; 2-ethylhexylglycidyl ether; allyl glycidyl ether;
cyclohexane oxide; and styrene oxide.

A process of preparing an antistatic polymeric composition comprising:

a) adding polymeric material selected from copolymers of styrene and acrylonitrile; terpolymers of
alpha-methylstyrene and acrylonitrile and copolymers of styrene and acrylonitrile; diene rubber;
copolymers of styrene and acrylontrile modified with acrylate elastomers; copolymers of styrene and
acrylonitrile modified with ethylene propylenediene monomer rubber; polystyrene and rubber modi-
fied impact polystyrene; polycarbonates, thermoplastic polyesters including polybutylene tereph-
thalate, polyethylene terephthalate and polyether-ester block copolymers; polyurethane; thermoplas-
tic polyurethane; polyphenylene oxide; polyacetals; polymethyl methacrylate; and mixtures thereof
and their polymer blends, said polymeric material is in the range from 70 to 97% by weight of said
antistatic polymeric composition to an effective amount of solid antistatic additive consisting of an
ethylene oxide copolymer having a dilution solution viscosity of greater than 0.25, said copolymer
excluding epihalohydrin; and

30
 EP 0 287 092 B1

b) mixing said polymeric material and said ethylene oxide copolymer to produce an antistatic
polymeric composition, wherein said ethylene oxide copolymer comprises:
a) ethylene oxide in the range of from 5 to 95% by weight of the ethylene oxide copolymer; and
b) at least one cyclic comonomer in the range of from 95 to 5% by weight of the ethylene oxide
copolymer, selected from alkylene oxide containing up to 25 carbon atoms represented by the
formula:

wherein Ri , R2, R3, and R+ selected from the group consisting of hydrogen, saturated aliphatic,
cycloaliphatic, monoolefinic aliphatic and cycloaliphatic, diolefinic (conjugated and non-conjugated)
aliphatic and cycloaliphatic, aromatic, and aralkyl, alkaryl; and at least one of R1 , R2, R3, and R+ is
not hydrogen,
said ethylene oxide copolymer having a weight average molecular weight from 20,000 to 5,000,000.

5. The process of claim 4 , wherein said ethylene oxide copolymer is in the range from 3 to 30% by
weight of said antistatic polymeric composition.

6. The process of claim 4 , wherein said alkylene oxide is selected from propylene oxide; 1,2-butylene
oxide; 1,2-dodecylene oxide; n-butylglycidyl ether; 2-ethylhexylglycidyl ether; allylglycidyl ether;
cyclohexane oxide; and styrene oxide.

Patentanspruche

1. Antistatische polymere Zusammensetzung, bestehend aus

a) wenigstens einem antistatischen Additiv aus einem Ethylenoxid-Copolymer im Bereich von 3 bis
30 Gew.-%, wobei das antistatische Ethylenoxid-Copolymer ein nicht-ionisches, bei Raumtemperatur
testes Material mit einer Viskositat in verdunnter Losung groBer als 0,25 g/ml ist, bestimmt an einer
Losung von 0,25 g des Polymers in 100 g Toluol mit einem Kapillarviskosimeter bei 25 °C gemaB
ASTM D2857, wobei das Copolymer Epihalogenhydrin ausschlieBt; und
b) einem Polymer, das aus Copolymeren von Styrol und Acrylnitril; Terpolymeren von Styrol,
Acrylnitril und Dien-Kautschuk; mit Acryl-Elastomeren modifizierten Copolymeren von Styrol und
Acrylnitril; mit Ethylen-Propylen-Dien-Monomer-Kautschuk modifizierten Copolymeren von Styrol und
Acrylnitril; Polystyrol und mit Kautschuk schlagfest gemachtem Polystyrol; Polycarbonaten; thermo-
plastischen Polyestern, einschlieBlich Polybutylenterephthalat, Polyethylenterephthalat und
Polyetherester-Block-Copolymeren; Polyurethan; thermoplastischem Polyurethan; Polyphenylenoxid;
Polyacetalen; Polymethylmethacrylat; und deren Mischungen und deren polymeren Gemengen
ausgewahlt ist, im Bereich von 70 bis 97 Gew.-%,
wobei das Ethylenoxid-Copolymer
a) Ethylenoxid im Bereich von 5 bis 95 Gew.-% und
b) wenigstens ein cyclisches Comonomer umfaBt, das aus einem bis zu 25 Kohlenstoff-Atomen
umfassenden Alkylenoxid der Formel

31
 EP 0 287 092 B1

ausgewahlt ist, worin

Ri , R2, R3 und R4 aus Wasserstoff, gesattigten Aliphaten, Cycloaliphaten, monoolefinischen Alipha-
ten und Cycloaliphaten, diolefinischen (konjugierten und nicht-konjugierten) Aliphaten und Cycloali-
phaten, Aromaten und Aralkylen und Alkarylen ausgewahlt sind und wenigstens einer der Substitu-
5 enten R1 , R2, R3 und R+ nicht Wasserstoff ist,
wobei das cyclische Comonomer im Bereich von 95 bis 5 Gew.-% des Ethylenoxid-Copolymers liegt;
wobei das Ethylenoxid-Copolymer ein Gewichtsmittel des Molekulargewichts von 20 000 bis 5 000 000
hat.

10 2. Zusammensetzung nach Anspruch 1, worin das Ethylenoxid-Copolymer ein bei Raumtemperatur testes
Material mit einer logarithmischen Viskositatszahl im Bereich von 0,25 bis 15,0 ist.

3. Zusammensetzung nach Anspruch 1, worin das Alkylenoxid aus Propylenoxid; 1,2-Butylenoxid; 1,2-
Dodecylenoxid; n-Butyl-glycidylether; 2-Ethylhexylglycidylether; Allylglycidylether; Cyclohexanoxid; und
15 Styroloxid ausgewahlt ist.

4. Verfahren zur Herstellung einer antistatischen polymeren Zusammensetzung, umfassend

a) das Hinzufugen eines polymeren Materials, das aus Copolymeren von Styrol und Acrylnitril;
Terpolymeren von a-Methylstyrol und Acrylnitril und Copolymeren von Styrol und Acrylnitril; Dien-
20 Kautschuk; mit Acryl-Elastomeren modifizierten Copolymeren von Styrol und Acrylnitril; mit Ethylen-
Propylen-Dien-Monomer-Kautschuk modifizierten Copolymeren von Styrol und Acrylnitril; Polystyrol
und mit Kautschuk schlagfest gemachtem Polystyrol; Polycarbonaten; thermoplastischen Polyestern,
einschlieBlich Polybutylenterephthalat, Polyethylenterephthalat und Polyetherester-Block-Copolyme-
ren; Polyurethan; thermoplastischem Polyurethan; Polyphenylenoxid; Polyacetalen; Polymethylme-
25 thacrylat; und deren Mischungen und deren polymeren Gemengen ausgewahlt ist, wobei das
polymere Material im Bereich von 70 bis 97 Gew.-% der antistatischen polymeren Zusammenset-
zung liegt, zu einer wirksamen Menge eines aus einem Ethylenoxid-Copolymer mit einer Viskositat
in verdunnter Losung groBer als 0,25 bestehenden festen antistatischen Additiv, wobei das Copoly-
mer Epihalogenhydrin ausschlieBt; und
30 b) das Vermischen des polymeren Materials und des Ethylenoxid-Copolymers zur Bildung einer
antistatischen Zusammensetzung,
wobei das Ethylenoxid-Copolymer
a) Ethylenoxid im Bereich von 5 bis 95 Gew.-% des Ethylenoxid-Copolymers und
b) wenigstens ein cyclisches Comonomer im Bereich von 95 bis 5 Gew.-% des Ethylenoxid-
35 Copolymers umfaBt, das aus einem bis zu 25 Kohlenstoff-Atomen umfassenden Alkylenoxid der
Formel

Rj R3

45
ausgewahlt ist, worin
R1 , R2, R3 und R4 aus der aus Wasserstoff, gesattigten Aliphaten, Cycloaliphaten, monoolefinischen
Aliphaten und Cycloaliphaten, diolefinischen (konjugierten und nicht-konjugierten) Aliphaten und
Cycloaliphaten, Aromaten und Aralkylen und Alkarylen bestehenden Gruppe ausgewahlt sind und
50 wenigstens einer der Substituenten R1 , R2, R3 und R+ nicht Wasserstoff ist,
wobei das Ethylenoxid-Copolymer ein Gewichtsmittel des Molekulargewichts von 20 000 bis 5 000 000
hat.

5. Verfahren nach Anspruch 4, worin das Ethylenoxid-Copolymer im Bereich von 3 bis 30 Gew.-% der
55 antistatischen polymeren Zusammensetzung liegt.

6. Verfahren nach Anspruch 4, worin das Alkylenoxid aus Propylenoxid; 1,2-Butylenoxid; 1,2-Dodecylen-
oxid; n-Butyl-glycidylether; 2-Ethylhexylglycidylether; Allylglycidylether; Cyclohexanoxid; und Styroloxid

32
 EP 0 287 092 B1

ausgewahlt ist.

Revendicatlons

5 1. Composition polymerique antistatique constitute de :

(a) au moins un additif antistatique d'un copolymere d'oxyde d'ethylene dans un intervalle allant de
3 a 30% en poids, ledit copolymere d'oxyde d'ethylene antistatique etant une matiere solide non-
ionique a la temperature ambiante ayant une viscosite en solution diluee superieure a 0,25 g/ml
ceci etant determine sur une solution constitute avec 0,25 g de polymere dans 100 de toluene
io avec un viscosimetre capillaire a 25 ° C selon ASTM D2857, ledit copolymere excluant I'epihalohydri-
ne ; et
(b) une matiere polymerique choisie parmi les copolymeres de styrene et d'acrylonitrile ; les
terpolymeres de styrene, d'acrylonitrile et de caoutchouc diene ; les copolymeres de styrene et
d'acrylonitrile modifies avec des elastomeres d'acrylate ; les copolymeres de styrene et d'acrylonitri-
15 le modifies avec un caoutchouc monomere d'ethylene-propylene-diene ; le polystyrene et le
polystyrene a impact modifie par du caoutchouc ; les polycarbonates, les polyesters thermoplasti-
ques incluant le terephtalate de polybutylene, le terephtalate de polyethylene et les copolymeres
sequences de polyether-ester ; le polyurethane ; le polyurethane thermoplastique ; I'oxyde de
polyphenylene ; les polyacetals ; le polymethacrylate de methyle ; et leurs melanges et melanges
20 polymeriques dans un intervalle allant de 70 a 97% en poids, ou ledit copolymere d'oxyde
d'ethylene comprend :
(a) de I'oxyde d'ethylene dans un intervalle allant de 5 a 95% en poids ; et
(b) au moins un comonomere cyclique choisi parmi un oxyde d'alkylene contenant jusqu'a 25
atomes de carbone represents par la formule

30

dans laquelle Ri , R2, R3 et R+ sont choisis parmi I'hydrogene, les groupes aliphatiques et
35 cycloaliphatiques satures, aliphatiques et cycloaliphatiques monoolefiniques, aliphatiques et cycloali-
phatiques diolefiniques (conjugues et non-conjugues), aromatiques, et aralkyles, alcaryles ; et au
moins I'un des radicaux R1 , R2, R3, et R+ n'est pas un hydrogene ; ledit comonomere cyclique est
dans un intervalle allant de 95 a 5% en poids du poids total dudit copolymere d'oxyde d'ethylene ;
ledit copolymere d'oxyde d'ethylene ayant un poids moleculaire moyen en poids allant de 20
40 000 a 5 000 000.

2. Composition de la revendication 1, dans laquelle ledit copolymere d'oxyde d'ethylene est une matiere
solide a la temperature ambiante et a une viscosite inherente dans un intervalle allant de 0,25 a 15,0.

45 3. Composition de la revendication 1, dans laquelle ledit oxyde d'alkylene est choisi parai I'oxyde de
propylene ; I'oxyde de 1,2-butylene ; I'oxyde de 1,2-dodecylene ; Tether glycidylique de n-butyle ;
Tether glycidylique de 2-ethylhexyle ; Tether glycidylique d'allyle ; I'oxyde de cyclohexane ; et I'oxyde
de styrene.

50 4. Procede de preparation d'une composition polymerique antistatique comprenant :

(a) Taddition d'une matiere polymerique choisie parmi les copolymeres de styrene et d'acrylonitrile ;
les terpolymeres d'alpha-methylstyrene et d'acrylonitrile et les copolymeres de styrene et d'acryloni-
trile ; le caoutchouc diene ; les copolymeres de styrene et d'acrylonitrile modifies avec des
elastomeres d'acrylate ; des copolymeres de styrene et d'acrylonitrile modifies avec un caoutchouc
55 monomere d'ethylene-propylene-diene ; le polystyrene et le polystyrene a impact modifie par du
caoutchouc ; les polycarbonates ; les polyesters thermoplastiques incluant le terephtalate de
polybutylene ; le terephtalate de polyethylene et les copolymeres sequences polyether-ester ; le
polyurethane, le polyurethane thermoplastique ; I'oxyde de polyphenylene ; les polyacetals ; le

33
 EP 0 287 092 B1

methacrylate de polymethyle ; et leurs melanges et melanges polymeriques, ladite matiere polyme-

rique etant dans un intervalle allant de 70 a 97% en poids de ladite composition polymerique
antistatique, a une quantite efficace d'additif antistatique solide constitue d'un copolymere d'oxyde
d'ethylene ayant une viscosite en solution diluee superieure a 0,25, ledit copolymere excluant
I'epihalohydrine ; et
(b) le melange de ladite matiere polymerique et dudit copolymere d'oxyde d'ethylene pour produire
une composition polymerique antistatique, ou ledit copolymere d'oxyde d'ethylene comprend :
(a) de I'oxyde d'ethylene dans un intervalle allant de 5 a 95% en poids du copolymere d'oxyde
d'ethylene ; et
(b) au moins un comonomere cyclique dans un intervalle allant de 95 a 5% en poids du copolymere
d'oxyde d'ethylene, choisi parmi les oxydes d'alkylene contenant jusqu'a 25 atomes de carbone
represented par la formule

dans laquelle Ri , R2, R3 et R+ sont choisis dans le groupe constitue par I'hydrogene, les groupes
aliphatiques et cycloaliphatiques satures, aliphatiques et cycloaliphatiques monoolefiniques, aliphati-
ques et cycloaliphatiques diolefiniques (conjugues et non-conjugues), aromatiques et aralkyles,
alkaryles ; et au moins un des radicaux R1 , R2, R3 et R+ n'est pas un hydrogene,
ledit copolymere d'oxyde d'ethylene ayant un poids moleculaire moyen en poids allant de 20
000 a 5 000 000.

Procede de la revendication 4 dans lequel ledit copolymere d'oxyde d'ethylene est dans un intervalle
allant de 3 a 30% en poids de ladite composition polymerique antistatique.

Procede de la revendication 4, dans lequel ledit oxyde d'alkylene est choisi parmi I'oxyde de propylene
; I'oxyde de 1,2-butylene ; I'oxyde de 1,2-dodecylene ; Tether glycidylique de n-butyle ; Tether
glycidylique de 2-ethylhexyle ; Tether glycidylique d'allyle ; I'oxyde de cyclohexane et I'oxyde de
styrene.

34