U.S. patent application number 10/383669 was filed with the patent office on 2003-09-04 for halogen containing polymer compounds containing modified zeolite stabilizers.
This patent application is currently assigned to Noveon IP Holdings Corp.. Invention is credited to Backman, Arthur L., Detterman, Robert E., Hamerly, Nancy A., Lepilleur, Carole A., Mazany, Anthony M., Milenius, David L..
Application Number | 20030166752 10/383669 |
Document ID | / |
Family ID | 24079981 |
Filed Date | 2003-09-04 |
United States Patent
Application |
20030166752 |
Kind Code |
A1 |
Detterman, Robert E. ; et
al. |
September 4, 2003 |
Halogen containing polymer compounds containing modified zeolite
stabilizers
Abstract
The present invention relates to a halogen containing polymer
compound containing a modified zeolite stabilizer. The modified
zeolite stabilizer has a small particle diameter, narrow particle
size distribution and less than 10 weight percent water. The
modified zeolite stabilizer is formed by shock annealing, coating
or a combination of the two methods.
Inventors: |
Detterman, Robert E.;
(Medina, OH) ; Hamerly, Nancy A.; (Brecksville,
OH) ; Lepilleur, Carole A.; (Akron, OH) ;
Mazany, Anthony M.; (Akron, OH) ; Milenius, David
L.; (Rocky River, OH) ; Backman, Arthur L.;
(Brecksville, OH) |
Correspondence
Address: |
Noveon, Inc.
Legal Department
9911 Brecksville Road
Cleveland
OH
44141-3247
US
|
Assignee: |
Noveon IP Holdings Corp.
Cleveland
OH
|
Family ID: |
24079981 |
Appl. No.: |
10/383669 |
Filed: |
March 7, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10383669 |
Mar 7, 2003 |
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09522221 |
Mar 9, 2000 |
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6531526 |
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09522221 |
Mar 9, 2000 |
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09151407 |
Sep 10, 1998 |
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6306945 |
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Current U.S.
Class: |
524/164 ;
524/178; 524/179; 524/180; 524/442 |
Current CPC
Class: |
C08L 57/08 20130101;
C08L 57/08 20130101; C08K 9/00 20130101; C08K 5/57 20130101; C08K
3/34 20130101; C08K 3/34 20130101; C08K 9/00 20130101 |
Class at
Publication: |
524/164 ;
524/178; 524/179; 524/180; 524/442 |
International
Class: |
C08K 005/58 |
Claims
We claim:
1. A halogen containing compound comprising a halogen containing
polymer and a modified zeolite stabilizer.
2. A halogen containing compound as claimed in claim 1, wherein
said modified zeolite stabilizer has a mean particle diameter in
the range of 0.25 to about 1.5 microns.
3. A halogen containing compound as claimed in claim 1, wherein
said modified zeolite stabilizer has a <90% value particle
diameter of about 0.30 to about 3 microns.
4. A halogen containing compound as claimed in claim 1, wherein
said modified zeolite stabilizer has a water content of less than
10 weight percent.
5. A halogen containing compound as claimed in claim 1, wherein
said halogen containing polymer is chosen from the group consisting
essentially of polyvinyl chloride, chlorinated polyvinyl chloride,
polyvinylidene chloride, polyvinyl bromide, polyvinyl fluoride,
polyvinylidene fluoride, copolymers of vinyl chloride with a
copolymerizable ethylenically unsaturated monomer, vinyl acetate,
vinyl butyrate, vinyl benzoate, alkyl fumarates and maleates, vinyl
propionate, alkyl acrylates, alkyl methacrylates, methyl
alpha-chloracrylates, styrene, vinyl ethers, vinyl ketones,
acrylonitrile, chloroacrylonitrile, allylidene diacetate,
chloroallylidene diacetate, ethylene and propylene and any
combinations of the foregoing.
6. A halogen containing compound as claimed in claim 5, wherein
said halogen containing polymer is chlorinated polyvinyl
chloride.
7. A halogen containing polymer as claimed in claim 5, wherein said
halogen containing polymer is polyvinyl chloride.
8. A halogen containing polymer as claimed in claim 1 wherein said
modified zeolite is present in an amount from about 0.5 to about 10
parts per hundred halogen containing resin.
9. A halogen containing polymer as claimed in claim 6, having a
dynamic thermal stability at 220 degrees C. of about 10 to about 60
minutes.
10. A halogen containing polymer as claimed in claim 6 having a
Notched Izod in the range of about 1.0 to about 20 (ft.lb/in.).
11. A halogen containing polymer as claimed in claim 6, having a
heat distortion temperature in the range of about 80.degree. C. to
about 140.degree. C. degrees.
12. A halogen containing polymer as claimed in claim 6, having
tensile strength in the range of about 5,000 to about 10,000
psi.
13. A halogen containing polymer as claimed in claim 1, wherein
said modified zeolite is a hydrated silicate of aluminum and
sodium.
14. A halogen containing polymer as claimed in claim 13, wherein
modified zeolite has a reduced water content.
15. A halogen containing polymer as claimed in claim 14, wherein
said reduced water content is content due to shock annealing.
16. A halogen containing polymer as claimed in claim 14, wherein
said reduced water content is content due to a coating on said
modified zeolite.
17. A halogen containing polymer as claimed in claim 1, wherein
said dynamic thermal stability is increased about 10% to about 300%
over a control.
18. A method of forming a stabilized halogen containing compound
comprising: mixing a halogen containing resin with a modified
zeolite stabilizer.
19. A method of forming a stabilized halogen containing compound as
claimed in claim 18, wherein said wherein said modified zeolite
stabilizer has a mean particle diameter in the range of 0.25 to
about 1.5 microns.
20. A method according to claim 18, wherein said modified zeolite
stabilizer has a <90% value particle diameter of about 0.30 to
about 3 microns.
21. A method according to claim 18, wherein said modified zeolite
stabilizer has a water content of less than 10 weight percent.
22. A method according to claim 18, wherein said halogen containing
polymer is chosen from the group consisting essentially of
polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene
chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene
fluoride, copolymers of vinyl chloride with a copolymerizable
ethylenically unsaturated monomer, vinyl acetate, vinyl butyrate,
vinyl benzoate, alkyl fumarates and maleates, vinyl propionate,
alkyl acrylates, alkyl methacrylates, methyl alpha-chloracrylates,
styrene, vinyl ethers, vinyl ketones, acrylonitrile,
chloroacrylonitrile, allylidene diacetate, chloroallylidene
diacetate, ethylene and propylene and any combinations of the
foregoing.
23. A method according to claim 22, wherein said halogen containing
polymer is chlorinated polyvinyl chloride.
24. A method according to claim 22, wherein said halogen containing
polymer is polyvinyl chloride.
25. A method according to claim 18, wherein said modified zeolite
is present in an amount from about 0.5 to about 10 parts per
hundred halogen containing resin.
26. A method according to claim 23, wherein said halogen containing
compound with the modified zeolite has a dynamic thermal stability
at 220.degree. C. of about 10 to about 60 minutes.
27. A method according to claim 23, wherein said halogen containing
compound with the modified zeolite has a notched izod in the range
of about 1.0 to about 20 ft.lb./in.
28. A method according to claim 23, wherein said halogen containing
compound with the modified zeolite has a heat distortion
temperature in the range of about 80.degree. C. to about
140.degree. C. degrees.
29. A method according to claim 23, wherein said halogen containing
compound with the modified zeolite has a tensile strength in the
range of about 5,000 to about 10,000 psi.
30. A method according to claim 18, wherein said modified zeolite
is a hydrated silicate of aluminum and sodium.
31. A method according to claim 18, wherein said modified zeolite
is shock annealed.
32. A method according to claim 18, wherein said modified zeolite
is coated with an inorganic, organic, or low molecular weight
coating in order to prevent water from entering zeolite.
33. A method according to claim 33, wherein said coating is
polymethyl siloxane.
34. A method according to claim 33, wherein said coating is dibutyl
thioglycolate.
35. A halogen containing compound wherein said modified zeolite
stabilizer is found in the range of 0.5 parts to 10 parts per 100
parts of halogen containing polymer.
36. A halogen containing compound according to claim 1, wherein
said modified zeolite is present in an amount of at least 0.05
parts per hundred parts of halogen containing resin.
37. A halogen containing compound according to claim 1 further
comprising a tin stabilizer.
38. A halogen containing compound according toclaim 37 comprising a
stabilizer selected from a group consisting of an alkyl tin maleate
stabilizer, an alkyl tin thioglycolate stabilizer, and mixtures
thereof.
39. A halogen containing compound according toclaim 38, whererin
the said halogen containing polymer is polyvinyl chloride and the
tin stabilizer is an alkyl tin thioglycolate.
40. A halogen containing compound according to claim 38, wherein
the said halogen containing polymer is chlorinated polyvinyl
chloride and the tin stabilizer is an alkyl tin maleate.
Description
[0001] This application is a continuation-in-part application from
U.S. application Ser. No. 09/151,407, which was filed on Sep. 10,
1998 and which is currently pending.
FIELD OF INVENTION
[0002] This invention relates to halogen containing polymer
compounds. In particular, the invention relates to halogen
containing polymers stabilized by modified zeolites. The modified
zeolites have a small particle size, narrow particle size
distribution, and a reduced water content. When incorporated into a
halogen containing compound, the modified zeolites improve the
processing stability of the compound and do not adversely diminish
its physical properties. Furthermore, the invention relates to a
halogen containing polymer compound stabilized by a modified
zeolite and having improved processing stability. Moreover, this
invention relates to a method of forming such a halogen containing
polymer compound incorporating a modified zeolite therein.
BACKGROUND OF THE INVENTION
[0003] Halogen containing polymers tend to degrade or deteriorate
when processed. Generally, the difference between the processing
temperature and the degradation temperature is very small.
Therefore, there is a risk that during the processing of these
halogen containing polymers, that the polymer will degrade. When
such polymers degrade, it is believed that the halide acid
generated by the polymer attacks the components of the processing
equipment. Also, this acid further catalyzes elimination reactions
and additional degradation of the polymer.
[0004] Stabilizers have been developed to help deter such
degradation. For example, organic compounds are commonly used. In
some instances, zeolites have also been used as stabilizers.
[0005] Zeolites are effective acid scavengers for halogen
containing polymers and enhance the thermal stability of halogen
containing polymers. Acid scavengers are compounds that react with
acids to form a compound that is typically chemically inert.
However, the use of zeolites as stabilizers or acid scavengers in
halogen containing polymer compounds has been limited for several
reasons. First, the zeolites generally have a large particle size,
generally in the range of about 3 to about 6 microns. The large
size of the zeolite particles not only causes surface blemishes on
the finish of the end product made from such a polymer but also
diminishes the physical properties of such polymers. Further,
outgassing occurs frequently with polymers containing zeolites when
the polymer is heated during processing due to the evolution of
water from the zeolite during the heating. As a result, there is
foaming.
[0006] U.S. Pat. No. 4,000,100 discloses a thermal and light
stabilized polyvinyl chloride resin. The stabilizer used in the
composition comprises an unactivated zeolite A molecular sieve or
an unactivated naturally occurring molecular sieve of essentially
the same pore size range as zeolite A and a conventional inorganic,
organometallic or organic stabilizer. The unactivated zeolite
molecular sieve has adsorbed water molecules. According to the
patentee, the combination of the unactivated zeolite and the
conventional stabilizer produces a compound with allegedly improved
stability as compared to a compounds produced with either of the
two stabilizers separately.
[0007] Similarly, U.S. Pat. No. 4,338,226 discloses a process for
the stabilization of polyvinyl chloride and stabilizer
compositions. The patent describes admixing sodium aluminosilicate
of small particle size (preferably, 0.1 to 20 microns), calcium
salts of fatty acids, zinc salts of fatty acids, partial esters of
polyols and fatty acids, thioglycolic acid esters of polyols and
polyvinyl chloride or copolymer of vinyl chloride. An
aluminosilicate that can be used is crystalline sodium zeolite A.
The composition is used for molding mixtures.
[0008] U.S. Pat. No. 4,371,656 describes a metal substituted
zeolite for use as a stabilizer for halogen containing resins. The
stabilizer comprises a crystalline aluminosilicate substituted with
ions of metallic elements belonging to Group II or Group IVA of the
Periodic Table for the Group I (M) metal ion contained in the
aluminosilicate. The stabilizer also must contain 10% by weight or
less as M.sub.2O of residual Group I metal ions. The stabilizer,
zeolite A, according to the patentee claims to have a water content
of 8% by weight or less. This patent also discloses the use of
organic substances to cover the voids of the zeolite particles and
prevent moisture reabsorption.
[0009] Stabilized chloride containing resins are also described in
U.S. Pat. No. 5,004,776. The stabilizer consists essentially of:
(a) an overbased alkaline earth metal carboxylate or phenolate
complex;(b) zeolite;(c) calcium hydroxide; and (d) a complex of at
least one metal perchlorate selected from the group consisting of
sodium, magnesium, calcium, and barium perchlorates with at least
one compound selected from the group consisting of polyhydric
alcohols and their derivatives. This stabilizer apparently prevents
the discoloration and deterioration in physical properties of the
chlorine containing resin resulting from thermal degradation when
the resin is subject to thermoforming or exposed to a high
temperature atmosphere for a long period of time.
[0010] Stabilizer compositions for use in halogen containing
polymer are also described in U.S. Pat. No. 5,216,058. The
stabilizer composition comprises hydrotalcite and a molecular sieve
zeolite. The molecular sieve zeolite comprises a Group IA or IIA
aluminosilicate.
[0011] U.S. Pat. No. 5,582,873 discloses an acid scavenger
stabilized halogen containing organic polymer. The patent also
describes the method for processing such a polymer. The composition
comprises a halogen containing polymer, an zeolite as the acid
scavenger and a heat stabilizer selected from the group consisting
of mixed metal stabilizers, organtotin stabilizers, lead
stabilizers, metal free stabilizers or any combination thereof. The
acid scavengers are sodium zeolites which have a 13 to 25% water
content, and a mean particle size of about 3 to about 5
microns.
[0012] Thus, there currently exists a need for a halogen containing
polymer compound having improved process stability. In particular,
a need exists for a stabilizer for a halogen containing compound
comprising a modified zeolite which maintains the physical
properties of the halogen containing polymer. More particularly, a
need exists for a modified zeolite stabilizer for use in
chlorinated polyvinyl chloride and polyvinyl chloride compounds.
More particularly, there exists a need for a chlorinated polyvinyl
chloride compound which has improved processability including
excellent heat stability.
SUMMARY OF THE INVENTION
[0013] The present invention comprises novel halogen containing
compounds with improved process stability. These compounds are made
from a halogen containing polymer and a modified zeolite. The
modified zeolite has a small particle size, a narrow particle size
distribution and a water content of less than 10 weight percent.
Furthermore, the present invention also comprises a method of
forming such a compound.
DETAILED DESCRIPTION
[0014] As described above, the present invention comprises a
composition of a halogen containing polymer and a modified zeolite,
wherein such modified zeolite imparts stability to the halogen
containing polymer and widens the range of temperatures which can
be used in the processing of such halogen containing compounds.
When incorporated into the compound, the modified zeolite does not
contribute to the deterioration of the physical properties of the
compound.
[0015] Examples of possible halogen containing polymers that can be
used in the instant invention include polyvinyl chloride,
chlorinated polyvinyl chloride, polyvinylidene chloride, polyvinyl
bromide, polyvinyl fluoride, polyvinylidene fluoride, copolymers of
vinyl chloride with a copolymerizable ethylenically unsaturated
monomer such as vinylidenechloride, vinyl acetate, vinyl butyrate,
vinyl benzoate, diethyl fumarate, diethyl maleate, other alkyl
fumarates and maleates, vinyl propionate, methyl acrylate,
2-ethylhexylacrylate, butyl acrylate, ethyl acrylate, and other
alkyl acrylates, methyl methacrylate, ethyl methacrylate, butyl
methacrylate, hydroxyethyl methacrylate, and other alkyl
methacrylates, methyl alpha-chloracrylates, styrene, vinyl ethers
such as vinyl ethyl ether, vinyl chloroethyl ether, vinyl phenyl
ether, vinyl ketones such as vinyl methyl ketone, vinyl phenyl
ketone, 1-fluoro-1-chloroethylene, acrylonitrile,
chloroacrylonitrile, allylidene diacetate, chloroallylidene
diacetate, ethylene and propylene and polymer blends such as blends
of polyvinyl chloride and polyethylene, polyvinyl chloride and
chlorinated polyethylene, polyvinyl chloride and
polybutylmethacrylate and any combinations of the foregoing. The
amount of the halogen containing polymer contained in the compound
can range from about 70 to about 99 weight percent. However, the
exact amount of the halogen containing polymer used in the compound
is dependent upon its end use and is well within the purview of one
of ordinary skill in the art.
[0016] Preferably, the halogen containing polymer is either
polyvinyl chloride or chlorinated polyvinyl chloride. Most
preferably, the halogen containing polymer is chlorinated polyvinyl
chloride.
[0017] The polyvinyl chloride ("PVC") which can be used in the
present invention preferably has an inherent viscosity in the range
of 0.52 to 1.0; a fused density of about 1.35 grams/cubic
centimeter and a chlorine content of about 56.7%. The PVC resin can
be formed by mass, suspension or emulsion polymerization
techniques. Examples of suitable PVC resins which can be used to
form the halogen containing compounds of the instant invention
include Geon 103EPF76TR, 103 EPF76, 30, 110X440, 27 and 1023PF5
PVC; all available from The Geon Company.
[0018] The PVC polymers can be homopolymers or copolymers of
polyvinylchloride. These polymers generally have a density of about
1.40 grams/cubic centimeter. Copolymers of PVC are formed
predominately with PVC and other copolymers such as for example
vinyl acetate. Generally, the secondary monomer is present in the
range of five percent. A further discussion of PVC copolymers can
be found in Volume 1 of Encyclopedia of PVC, edited by Leonard I.
Nass, Marcel Dekker, Inc. (N.Y. 1976, Chap.4).
[0019] Alternatively, PVC compounds can also be used. Examples of
suitable PVC compounds include: Geon M6215 and M6230 rigid
injection molding PVC; Geon 85890 and 85891 cellular injection
molding PVC; Geon 8700A, 8700.times., 87256, and 87160 interior
rigid extrusion PVC; Geon 87416, 87703 and 6935 exterior rigid
extrusion PVC; and Geon 85893, 87344, 87345, 87538, 87695 and 87755
rigid powder extrusion PVC. The various grades of the Geon PVC are
commercially available from The Geon Company.
[0020] The most preferred halogen containing polymer used in the
compound of the instant invention is chlorinated polyvinyl
chloride. Chlorinated polyvinyl chloride ("CPVC") is known to have
excellent high temperature performance characteristics, among other
desirable physical properties. Typically, CPVC has an excess of 57%
bound chlorine. CPVC is conveniently made by the chlorination of a
polymer of vinyl chloride (PVC), which include both homopolymers
and copolymers of vinyl chloride, having a chlorine content of up
to 56.7%.
[0021] CPVC is obtained by chlorinating homopolymers or copolymers
of PVC containing less than fifty percent (50%) by weight of one or
more copolymerizable comonomers. Preferably, comonomers are not
used. However, suitable comonomers include acrylic and methacrylic
acids; esters of acrylic and methacrylic acid wherein the ester
portion has from 1 to 12 carbons; hydroxyalkyl esters of acrylic
and methacrylic acid (for example hydroxymethyl methacrylate,
hydroxyethyl acrylate, hydroxyethyl methacrylate and the like);
glycidyl ester of acrylic and methacrylic acid (for example
glycidyl acrylate, glycidyl methacrylate and the like);
alpha,beta-unsaturated dicarboxylic acids and their anhydrides (for
example maleic acid, fumaric acid, itaconic acid and the like);
acrylamide and methacrylamide; acrylonitrile and methacrylonitrile;
maleimides; olefins (for example ethylene, propylene, isobutylene,
hexene and the like); vinylidene halide; vinyl esters; vinyl
ethers; crosslinking monomers (for example, diallyl phthalate,
ethylene glycol dimethacrylate, methylene bis-acrylamide, divinyl
ether, allyl silanes and the like).
[0022] Any post chlorination processes can be used to form CPVC
polymer having more than fifty-seven percent (57%) by weight
chlorine based upon the total weight of the polymer. Preferably,
the CPVC polymer has a chlorine content in the range of about sixty
percent (60%) to about seventy four percent (74%) by weight based
upon the total weight of the polymer. The post chlorination
processes which can be used include any commercial process or the
like such as solution process, fluidized bed process, water slurry
process, thermal process or liquid chlorine process or two step
process which comprises post chlorinating the vinyl chloride
polymer in the presence of a peroxy catalyst during both steps. In
as much as the post chlorination processes are known to the art as
well as the literature, they will not be discussed in detail here.
Rather reference is hereby made to U.S. Pat. Nos. 2,996,049;
3,100,762; 4,412,898 3,532,612; 3,506,637; 3,534,013; 3,591,571;
4,049,517; 4,350,798; 4,377,459, 5,216,088 and 5,340,880 which are
hereby fully incorporated by reference as to the method of forming
CPVC by post chlorinating PVC. The preferred process in forming the
CPVC from the PVC is the aqueous suspension process disclosed in
U.S. Pat. No. 4,412,898.
[0023] In addition, blends of various CPVC resins can also be used.
For example, the CPVC resin can be blended with PVC homopolymers or
copolymers or with another CPVC resin in an amount of other resin
of about 1 weight percent to about 50 weight percent. Additionally,
the CPVC can also be blended from about 1 weight percent to about
50 weight percent with another other halogen containing polymer or
polymers.
[0024] The CPVC used in the invention desirably will have a fused
density in the range of approximately 1.38 to 1.65 grams/cubic
centimeter at 25.degree. Centigrade, an inherent viscosity (I.V.)
in the range of about 0.52 to about 1.0 and a chlorine content of
at least sixty percent (60%). The preferred fused density of the
CPVC resin is in the range of about 1.51 to about 1.65 grams/cubic
centimeter. The preferred inherent viscosity is in the range of
about 0.68 to about 0.92. The preferred chlorine content of the
CPVC is about 63% to about 70.5%. Examples of suitable CPVC resins
to use in forming the compound of the instant invention include
TempRite.RTM. 677x670 CPVC, and TempRite.RTM. 674x571 CPVC, all
available from The B. F. Goodrich Company. TempRite.RTM. is a
registered trademark of The B. F. Goodrich Company. The most
preferred CPVC resin is TempRite.RTM. 674x571 CPVC resin.
[0025] Alternatively, CPVC compounds can be used in the compounds
of the compound of the instant invention. Examples of suitable
compounds which can be used include the following TempRite.RTM.
CPVC compounds: 3104, 3210, 88038, 3107, 3109, 3114, 88738, 3105,
3214, 88971, 88027, 3219, 3205, 3212, 3206, 88023, 88033, 88955,
SP220, 88745 and 3207 CPVC compounds. TempRite.RTM. is a registered
trademark of The B. F. Goodrich Co. The above enumerated compounds
are all commercially available from The B. F. Goodrich Co. in
Cleveland, Ohio. The most preferred CPVC compound used in the
instant invention is TempRite.RTM. 3104 CPVC compound.
[0026] The halogen containing polymer is stabilized by an effective
amount of a modified zeolite. The modified zeolite should have a
narrow particle size distribution, small particle size, and a
reduced water content. Preferably, the zeolite should have a mean
particle diameter in the range of about 0.25 to about 1.5 microns,
a <90% value particle diameter (90% by weight of the particles
are of a particle diameter below the range) of about 0.30 to about
3 microns, and a water content of less than 10 weight percent.
[0027] Zeolites comprise basically of a three dimensional framework
of SiO4 and AlO.sub.4 tetrahedra. The tetrahedra are crosslinked
through the sharing of oxygen atoms so that the ratio of oxygen
atoms to the total of the aluminum and silicon atoms it equal to 2.
This relationship is expressed as O/(Al+Si)=2. The electrovalence
of the tetrahedra containing aluminum and silicon is balanced in
the crystal by the inclusion of a cation. For example, the cation
can be an alkali or alkaline earth metal ion. The cation can be
exchanged for another depending upon the final usage of the
aluminosilicate zeolite. The spaces between the tetrahedra of the
aluminosilicate zeolite are usually occupied by water. Zeolites can
be either natural or synthetic.
[0028] The basic formula for all aluminosilicate zeolites is
represented as follows:
M.sub.2/nO:
[Al.sub.2O.sub.3].sub.x:[SiO.sub.2].sub.y:[H.sub.2O].sub.z
[0029] wherein M represents a metal, n represents the valence of
the metal and X and Y and Z vary for each particular
aluminosilicate zeolite. Essentially it is believed that any
aluminosilicate zeolite can be used as a stabilizer in the instant
invention, provided that the ratio of the silicon to aluminum in
such aluminosilicate zeolite is less than 3.0 and that the
aluminosilicate zeolite can be incorporated into the halogen
containing polymer. Preferably, the zeolite ratio of silicon to
aluminum in such aluminosilicate zeolite is less than 1.5. Most
preferably, the ratio of silicon to aluminum in such
aluminosilicate zeolite is about 1.
[0030] It is further believed that the following zeolites which can
be used in the instant invention include but are not limited to
zeolite A, described in U.S. Pat. No. 2,822,243; zeolite X,
described in U.S. Pat. No. 2,822,244; zeolite Y, described in U.S.
Pat. No. 3,130,007; zeolite L, described in Belgian Patent No.
575,117 zeolite F, described in U.S. Pat. No. 2,996,358; zeolite B,
described in U.S. Pat. No. 3,008,803; zeolite M, described in U.S.
Pat. No. 2,995,423; zeolite H, described in U.S. Pat. No.
3,010,789; zeolite J, described in U.S. Pat. No. 3,011,869; and
zeolite W, described in U.S. Pat. No. 3,102,853.
[0031] The preferred zeolites include alone or in combination with
another Group I metal, hydrated silicates of aluminum incorporating
sodium, of the type
mNa.sub.2O.xAl.sub.2O.sub.3.ySiO.sub.2.zH.sub.2O. These preferred
zeolites include zeolites A, X, and Y. The most preferred zeolite
is zeolite 4A. Zeolite 4A, preferably has the following
formula:
M.sub.2/nO:[AlO.sub.2].sub.12:[SiO.sub.2].sub.12:[H.sub.2O].sub.27
[0032] wherein M is sodium. Any method can be used to form such
zeolite provided that the mean particle diameter of the zeolite is
less than 1.5 microns, and <90% value particle diameter of about
0.30 to about 3 microns. Furthermore, when modified, this zeolite
must have a water content of less than 10 weight percent and should
provide for improved process stability when incorporated into a
compound.
[0033] For example, a relatively simple process can be used to
prepare the zeolite of the instant invention. First, the zeolite is
synthesized. The exact synthesis will vary dependent upon the
specific zeolite being used; this synthesis is well within the
skill of one of ordinary skill in the art. Generally, however, a
mixture of the aqueous solution of the materials which can be
represented as mixtures of oxides, Na.sub.2O; Al.sub.2O.sub.3;
SiO.sub.2 and H.sub.2O are reacted at a temperature in the range of
about 50.degree. C. to about 100.degree. C. for a period of about
45 minutes to about 2000 minutes. Alternatively, the mixture of the
reactants are allowed to age from about 0.1 to 48 hours at ambient
conditions prior to the crystallization step. Preferably, the
temperature of the reaction is in the range of about 50.degree. C.
to about 80.degree. C. and the reaction is carried out for about 60
to 420 minutes. Most preferably, the temperature is 60.degree. C.
to 70.degree. C. with a reaction of time of 90 to 300 minutes. The
result of this reaction is a zeolite having a mean particle
diameter in the range of about 0.25 to 1.5 microns. The <90
percent particle diameter value is in the range of about 0.30 to
about 3.0 microns.
[0034] After the zeolite is formed, it is washed. The zeolite can
be washed with deionized water, filtered and dried at about 100 to
about 200.degree. C., then dehydrated at about 250 to about
500.degree. C. Any means available to dehydrate the zeolite can be
used. It is believed that the zeolite has better reproductivity if
dried. For example, the zeolite can be furnace dehydrated. If
furnace dehydrated, any suitable furnace can be used provided that
the desired temperature can be reached. Generally if furnace
dehydrated, the zeolite is heated to approximately 250 to about
500.degree. C. for about 2 to 6 hours. Alternatively, the small
particle size zeolite can be dehydrated in vacuo at approximately
200.degree. C. for about 2 to about 6 hours.
[0035] These aluminosilicate zeolites are then modified. The
modified aluminosilicate zeolite has a water content of less than
10 weight percent. Any method which decreases the water content of
the aluminosilicate zeolite can be used. For example, the
aluminosilicate zeolite can be modified by chemically altering the
surface of the zeolite particles, shock annealing or by a coating
or by a combination of shock annealing and coating processes. The
purpose of the modification is to prevent the aluminosilicate
zeolite particles from absorbing water but still allowing the
zeolite particles to react with the acid released upon the
deterioration or degradation of the halogen containing polymer. If
CPVC is the polymer used in the halogen containing compound,
preferably, the water content of the modified aluminosilicate
zeolite is less than 8 weight percent.
[0036] Any organic, inorganic or low molecular weight (<10,000)
coating or coating mixture can be used provided that it has the
following characteristics. First, in the case of inorganic
coatings, they cannot be redox active; namely, the composition
should have its d shell filled. Second, the coating cannot be water
soluble or water permeable. Third, the coating should be reactive
or permeable to the halogen acid. Fourth, the coating should not be
a Lewis Acid. Preferably the coating used is miscible with the
halogen containing polymer. Examples of suitable coatings include
oxides such as magnesium oxide, paraffin waxes, low molecular
weight organic matrices such as calcium stearate, high molecular
weight matrices such as siloxanes, acrylic polymers such as
methacrylate polymers. Preferably the coating is either dibutyl tin
thioglyocalate or polydimethysiloxane.
[0037] The coating can be prepared in situ during the formation of
the zeolite particles or applied to the zeolite particles in a
separate step. If applied in a separate step, care should be taken
to ensure the uniform application of the coating as well as to
avoid clumping. Furthermore, the coating cannot be too thick or too
thin, therefore, a balance must be obtained so as to ensure low
water absorption but retain activity of the zeolite particles as
acid scavenger.
[0038] Alternatively, the zeolite particles can be modified by
shock annealing the particles. With the use of a shock annealing
process for the zeolite particles, a phase transformation occurs at
the outer surface of the zeolite particle shell. It is believed
that the phase transformation causes the collapse of the zeolite
structure at the outer surface. The shock annealing occurs at a
temperature above the phase transformation temperature of the
zeolites followed by rapid cooling. The shock annealing is carried
out for the appropriate time to cause the outer surface of the
particles to collapse. Exposure time to this temperature above the
phase transformation temperature is however limited to minimize the
bulk absorption of thermal energy and to limit the phase
transformation to the outer surface of the particles. The
temperature at which the zeolite is heated during the shock
annealing process is dependent upon the particular zeolite being
shock annealed. The temperature as well as the time to shock anneal
is well within the skill of one of ordinary skill in the art.
[0039] One method to shock anneal the zeolite particles is
disclosed in the copending application filed by the instant
inventors, entitled "Zeolites and Method of Making Thereof", filed
concurrently herewith. The contents of the application are
incorporated in its entirety herein.
[0040] As described in the copending application, the zeolite
particles are then placed in a furnace during the shock annealing
step. Preferably, the particles are placed in a preheated crucible
which can be made from quartz, high temperature steels or aluminum
oxide. The crucible with the particles are returned to a muffle
furnace. Any furnace can be used so long as it reaches the desired
temperature. In the most preferred embodiment, an aluminum oxide
crucible is preheated to approximately 700 to 1200.degree. C. prior
to the addition of the small particle size zeolite.
[0041] Once the zeolite is added, it is heated about 1 to about 30
minutes in the temperature range of about 700 to about 1200.degree.
C. After the zeolite particles are heated, as set forth in further
detail in the copending application, they are cooled. Any cooling
means can be used so long as the temperature is cooled below the
phase transformation temperature in a matter of seconds, for
example, about 600.degree. C. for zeolite 4A. Therefore, the
particles can be cooled by air, water, carbon dioxide or liquid
nitrogen.
[0042] Alternatively, the zeolite particles can be modified by both
shock annealing and coating. If such a combination method is used
to modify the zeolite particles, they are first shock annealed to
within 15 to 10 percent of the desired optimum properties and then
coated. By using both a coating and the shock annealing step, it
may be possible to use other coatings which do not meet all the
listed parameters set forth above with respect to the coatings.
[0043] The amount of the modified zeolite added to the halogen
containing polymer to form the compounds of the instant invention
is generally in the amount of about 0.05, 0.1, 0.2, 0.25, 0.3, 0.5,
0.75, or 1 to about 10 per one hundred parts of halogen resin used
in the compound. Most preferably, the amount of modified zeolite
added to the compound is in the range of about 0.1, 0.2, 0.3, 0.4
to 7 weight percent of the compound. By adding the zeolite to the
compound, the dynamic thermal stability of the compound as measured
by ASTM D 2538 is increased from 10% to 300% compared to a control
compound without zeolite. Additionally, by adding the zeolite to
the compound a reduced amount of thermal stabilizer is needed to
maintain or increase dynamic thermal stability when compared to a
compound not containing the zeolite.
[0044] In addition to the halogen containing polymer and the
modified zeolite stabilizer, other ingredients typically added to
halogen containing polymers can be included in the compounds of the
instant invention. The amount and nature of these ingredients is
dependent upon the end use of the halogen containing polymer. The
ingredients and their amount can be tailored to meet the end-use
needs by one of ordinary skill in the art.
[0045] For example, other stabilizers can also be used in
conjunction with the modified zeolite stabilizer in the halogen
containing polymer of the instant invention depending upon the
halogen polymer used. Examples of possible stabilizers to use in
halogen containing polymers include tin stabilizers, lead
stabilizers, as well as stabilizers containing lithium, sodium,
potassium, magnesium, calcium, strontium, barium, zinc, cadmium,
aluminum, lead and antimony. Many of these enumerated stabilizers
fall into a group of stabilizers called metal soap stabilizers.
Metal soap stabilizers are metal carboxylates wherein the
carboxylic acid typically has a chain length of 8 to 18 carbon
atoms. Metal soap stabilizers can also include mixed metal soaps
stabilizers. Examples of some mixed metal soap stabilizers include
barium/cadmium, barium/cadmium/zinc, barium/zinc, barium/tin,
barium/lead, cadmium/zinc, calcium/zinc, calcium/zinc/tin,
strontium/zinc.
[0046] Suitable tin stabilizers include tin salts of monocarboxylic
acids such as stannous maleate. Examples of tin stabilizers include
without limitation: alkylstannoic acids, bis(dialkyltin alkyl
carboxylate)maleates, dialkyltin bis(alkylmaleates), dialkyltin
dicrotonates, dialkyltin diolates, dialkyltin laurates, dialkyltin
oxides, dialkyltin stearates, alkylchlorotin bis(alkylmercaptides),
alkylchlorotin bis (alkylmercaptopropionates), alkylthiostannoic
acids, alkyltin tris(alkylmercaptides), alkyltin
tris(alkylmercaptoacetates), alkyltin
tris(alkylmercaptopropionates), bis[dialkyl(alkoxycarbonylmethyl-
enethio)tin]sulfides, butyltin oxide sulfides, dialkyltin
bis(alkylmercaptides), dialkyltin bis(alkylmercaptoacetates),
dialkyltin bis(alkylmercaptopropionates), dialkyltin
.beta.-mercaptoacetates, dialkyltin .beta.-mercaptoacetates,
dialkyltin .beta.-mercaptopropionates- , dialkyltin sulfides,
dibutyltin bis(i-octyl maleate), dibutyltin bis(i-octyl
thioglycolate), dibutyltin bisthiododecane, dibutyltin
.beta.-mercaptopropionate, dimethyltin bis(i-octyl thioglycolate),
dioctyltin laurate, methyltin tris(i-octyl thioglycolate). Examples
of a commercially available tin stabilizer are Mark 292 and Mark
1900 stabilizers from Witco Chemical and Thermolite 31 stabilizer
from Elf Atochem.
[0047] Lead stabilizers can also be used in the halogen containing
compounds of the instant invention. Examples of lead stabilizers
are dibasic lead stearate, tribasic lead stearate, dibasic lead
phthalate, tribasic lead phosphite, basic lead silico-sulfate,
tribasic lead sulfate, tetrabasic lead sulfate and lead
carbonate.
[0048] Other co-stabilizers may be included in the compounds with
the stabilizers if such stabilizers are used in addition to the
modified zeolite stabilizer, and if desired, but are not necessary.
However, if a solid co-stabilizer is added, the particle size of
the co-stabilizer must be small enough so as not to affect the
impact properties of the compounds described herein. Examples of
co-stabilizers include metal salts of phosphoric acid, polyols,
epoxidized oils, beta-diketones and acid acceptors which are not
detrimental to the base halogen containing polymer used. The
stabilizers can be used by themselves or in any combination as
desired. Specific examples of metal salts of phosphoric acid
include water-soluble, alkali metal phosphate salts, disodium
hydrogen phosphate, orthophosphates such as mono-,di-, and
tri-orthophosphates of said alkali metals, alkali metal
polyphosphates, -tetrapolyphosphates and -metaphosphates and the
like. Polyols such as sugar alcohols, and epoxides such as
epoxidized soya oil can be used. Examples of possible acid
acceptors include potassium citrate, aluminum magnesium hydroxy
carbonate hydrate. An example of commercially available aluminum
magnesium hydroxy carbonate hydrate is Hysafe 510, available from
the J. M. Huber Company.
[0049] Chlorinated polyethylene (CPE) can also be added to the
halogen containing polymer compound stabilized by the modified
zeolite. The CPE is a rubbery material resulting from the
chlorination of polyethylene having a substantially linear
structure. The polyethylene can be chlorinated by various methods
including aqueous suspension, solution or gas phase methods. An
example of a method for preparing CPE can be found in U.S. Pat. No.
3,563,974. Preferably, the aqueous suspension method is used to
form the CPE. If used as an impact modifier, the CPE material
contains from 5 to 50% by weight of chlorine. Preferably, the CPE
contains from 25 to 45% by weight of chlorine. However, the CPE can
comprise a mixture of chlorinated polyethylenes, provided that the
overall mixture has a chlorine content in the range of about 25 to
45% by weight chlorine. CPE is commercially available from The
DuPont Dow Elastomer Company. The preferred CPE materials to be
used in the compound include Tyrin 361 IP, Tyrin 2000 and Tyrin
3615P; all available from the DuPont Dow Elastomer Company. Tyrin
is a trademark of the DuPont Dow Elastomer Company.
[0050] The modified zeolite stabilized halogen containing polymer
compound may also include acrylic impact modifiers. U.S. Pat. No.
3,678,133 describes the compositions conventionally referred to as
acrylic impact modifiers. Generally, the acrylic impact modifier is
a composite interpolymer comprising a multi-phase acrylic base
material comprising a first elastomeric phase polymerized from a
monomer mix comprising at least 50 wt. % alkyl methacrylate having
1-4 carbon atoms in the alkyl group and having a molecular weight
of from 50,000 to 600,000. Further, the patent states that the
polymerization of the rigid thermoplastic phase is preferably
conducted in such a fashion that substantially all of the rigid
phase material is formed on or near the surface of the elastomeric
phase. Acrylic impact modifiers are polyacrylates including
(C.sub.4-C.sub.12) acrylate homo or copolymers, second stage graft
copolymerized with methyl methacrylate and styrene, poly(ethylhexyl
acrylate-co-butyl-acrylate) graft copolymerized with styrene,
and/or acrylonitrile and/or methyl methacrylate; polybutyl acrylate
graft polymerized with acrylonitrile and styrene. Examples of
suitable acrylic impact modifiers include Paraloid EXL-2330, KM
330, KM 334, and KM 365; all of which are available from Rohm and
Haas. Paraloid is a trademark of the Rohm & Haas Company.
Additionally Durastrength 200, available from Elf Atochem, and Kane
Ace FM-10 and Kane Ace FM-25, available from Kaneka, are examples
of commercially available acrylic impact modifiers.
[0051] Methyl butadiene styrene ("MBS") impact modifiers can also
be added to the compounds of the present invention. MBS polymers
are graft polymers. Generally, MBS impact modifiers are prepared by
polymerizing methyl methacrylate or mixtures of methyl methacrylate
with other monomers in the presence of polybutadiene or
polybutadiene-styrene rubbers. Further information on MBS impact
modifiers can be found in the Second Edition of the Encyclopedia of
PVC, edited by Leonard I. Nass, Marcel Dekker, Inc. (N.Y. 1988, pp.
448-452). Examples of commercially available MBS impact modifiers
include Paraloid KM 680, BTA 733, BTA 751, BTA 753 available from
Rohm & Haas, Kane Ace B-22 impact modifier and Kane Ace B-56
impact modifier available from Kaneka.
[0052] Other additives can also be added to the halogen containing
polymer compounds as needed. Conventional additives known in the
art as well any other additives may be used, provided that the
additive does not alter the physical properties and the process
stability associated with the novel compounds. Examples of
additives which can be used include antioxidants, lubricants, other
stabilizers, other impact modifiers, pigments, glass transition
enhancing additives, processing aids, fusion aids, fillers, fibrous
reinforcing agents and antistatic agents. The amount and nature of
the additives incorporated into the halogen containing compounds
stabilized by the modified zeolite is well within the skill of one
of ordinary skill in the art.
[0053] Exemplary lubricants are polyglycerols of di- and
trioleates, polyolefins such as polyethylene, polypropylene and
oxidized polyolefins such as oxidized polyethylene and high
molecular weight paraffin waxes. Since several lubricants can be
combined in countless variations, the total amount of lubricant can
vary from application to application. Optimization of the
particular lubricant composition is not within the scope of the
present invention and can be determined easily by one of ordinary
skill in the art. Preferably, an oxidized polyethylene is used. An
example of an oxidized polyethylene is AC 629A, sold by Allied
Signal. In addition to the oxidized polyethylene, preferably a
paraffin wax is also included in the compounds of the instant
invention. An example of a paraffin wax is Paraffin 160F Prill from
Witco.
[0054] Suitable processing aids include acrylic polymers such as
methyl acrylate copolymers. Examples of process aids include
Paraloid K-120ND, K-120N, K-175; all available from Rohm &
Haas. A description of other types of processing aids which can be
used in the compound can be found in The Plastics and Rubber
Institute: International Conference on PVC Processing, April 26-28
(1983), Paper No. 17.
[0055] An example of antioxidants to be used in the halogen
containing compounds include Irganox 1010
(tetrakis[methylene(3,5-di-tert-butyl-4-hy-
droxy-hydrocinnamate)]methane) sold by Ciba, if used at all.
[0056] Suitable pigments include among others titanium dioxide, and
carbon black. Examples of titanium dioxide is Tiona RCL-6 and RCL-4
from Millenium Inorganics. An example of carbon black is Raven 410,
available from Columbian Chemicals.
[0057] Suitable inorganic fillers include talc, clay, mica,
wollastonite, silicas, and other filling agents.
[0058] The components of the unique compound can be made in any
manner wherein the various components are added together and mixed
under heat. For example, the appropriate amount of the halogenated
resin or halogen compound can be added to a vessel such as Henschel
mixer or a ribbon blender. The remaining ingredients of the
compound can then be added thereto and mixed until the blend is
homogeneous. If pellets are to be formed, the compound can be melt
mixed. Melt mixing can generally occur in the temperature range of
about 150 to about 250.degree. C., if CPVC is the halogenated resin
used as the base polymer to form the instant compound. Once the
blend is formed, it can be processed further depending upon the
desired application in any conventional manner, using extrusion or
molding techniques.
[0059] If extrusion techniques are used to process the composition
of the present invention, generally conventional extrusion
machinery such as a multi-screw extruder or a single screw extruder
are used. An extruder generally has conveying means, an
intermediate screw processing means and a final die through which
the material is discharged in the form of an extrudate. Generally,
a multi-screw extruder is used for the extrusion of pipe. Examples
of possible conventional extruders to be used to process the CPVC
and PVC compounds containing the modified zeolite include the
following twin screw counterrotating extruder models from
Cincinnati Milacron: CM 35HP, CM 55HP, CM 65HP, CM 80HP, CM 92HP.
Examples of suitable conical twin screw extruders from Krauss
Maffei include KMD-2/40KK and KMD-2/50KK.
[0060] If the halogen containing polymer compound contains CPVC and
is made according to the instant invention, it has the following
characteristics: a tensile strength in the range of about 5,000 to
about 10,000 psi (as measured according to ASTM D 638-95); a
Notched Izod in the range of about 1.0 to about 20 ft.lb. per inch
of notch (as measured according to ASTM D 256-93A); a dynamic
thermal stability in the range of about 10 to about 60 minutes as
measured by ASTM D 2538); a heat distortion temperature in the
range of about 80 to about 140.degree. C. (as measured by ASTM D
648-95). Generally, the compound containing the modified zeolite
maintains approximately 90% of its physical properties as compared
to the same compound without the modified zeolite. This novel
compound can be formed into any article desired. Examples include
but are not limited to sheet, pipe, ducts, fittings, valves,
injection molded and thermoformed industrial parts, appliance
housing, fabricated parts, and different containers.
[0061] The following non-limiting examples serve to further
illustrate the present invention in greater detail.
EXAMPLE I
[0062] A zeolite 4A powder was synthesized by individually
preparing the following solutions: a sodium silicate solution, a
sodium aluminate solution and a sodium hydroxide solution. The
sodium silicate solution was prepared by dissolving 255.6 grams of
Na.sub.2SiO.sub.3.9H.sub.2O in 650 grams of water. The sodium
aluminate solution was prepared by dissolving 270.0 grams of
NaAlO.sub.2 in 320 grams of water and the sodium hydroxide solution
was prepared by adding 500 grams of NaOH in 650 grams of water. An
additional solution of 10.0 grams of ZnCl.sub.2 and 90.0 grams of
water was also prepared. All solutions were maintained at about
55.degree. C. after all solids are dissolved. The sodium hydroxide
solution was then added with stirring to the sodium aluminate
solution. The resulting sodium aluminate/sodium hydroxide solution
was added concurrently with the zinc chloride solution to the
sodium silicate solution, again with stirring. The reaction
temperature was maintained at 60.degree. C. for 2 hours and then
filtered and rinsed. A zeolite 4A produced by this method exhibited
the following properties.
[0063] The particle size of the zeolite powder as determined using
a Coulter LS Particle Size Analyzer was as follows: a mean particle
diameter of 0.9 .mu.m and <90% value of 1.8 .mu.m.
[0064] A sample dehydrated at 350.degree. C. exhibited a weight
gain of 22% after 2 days of exposure to ambient conditions. In
contrast, most commercially available zeolites will exhibit a
moisture gain of about 18 to about 22 weight % within 48 hours.
[0065] The Dynamic Thermal Stability (DTS) measured according to
ASTM D 2538 of a TempRite.RTM. 3104 CPVC compound (commercially
available from The B. F. Goodrich Company) was evaluated with and
without the above zeolite using a Brabender torque rheometer set at
a 208.degree. C. bowl temperature, 35 rpm and a 70 gram loading.
The DTS time of the TempRite.RTM. 3104 CPVC control was 13 minutes
and with the addition of 3 parts per hundred resin (phr) of the
zeolite 4A prepared according to Example I to the TempRite.RTM.
3104 CPVC compound, the DTS time was increased to 36 minutes, a
157% increase over the control value. The DTS increase is defined
as (DTS.sub.zeolite containing-DTS.sub.control (no
zeolite)/DTS.sub.control.times.100%). A longer DTS time is
indicative of a compound with enhanced stability.
EXAMPLE II
[0066] A 20.0 gram portion of a dehydrated zeolite prepared
according to Example I was calcined by gradually heating to
840.degree. C. for one (1) hour and cooled to room temperature
gradually under vacuum. The resulting material exhibited virtually
no weight gain due to water uptake upon exposure to ambient
conditions for 500 hours. The DTS time of the TempRite.RTM. 3104
CPVC was unchanged upon addition of 3 phr of the calcined zeolite
(0% increase over control DTS value, indicating that the zeolite
has lost its reactivity under those calcination conditions).
EXAMPLE III
[0067] An 100 mL Al.sub.2O.sub.3 crucible was heated to 840.degree.
C. in a muffle furnace. The crucible was extracted from the furnace
and a 20.0 gram portion of a dehydrated zeolite prepared according
to Example I was added to the crucible which was then returned to
the furnace and heated for 15 minutes. The heated zeolite powder
was then poured into another crucible at room temperature
immediately after removal from the furnace. The resulting material
exhibited 0.7% weight gain due to water uptake upon exposure to
ambient conditions after 48 hours. The DTS time of the
TempRite.RTM. 3104 control was increased upon addition of 3 phr of
the shock-annealed zeolite from 13 minutes to 30 minutes (131%
increase over control DTS value).
EXAMPLES IV-XX
[0068] Another zeolite 4A powder was synthesized by individually
preparing the following solutions: (1) a sodium silicate solution;
(2) a sodium aluminate solution; and (3) and a sodium hydroxide
solution. The sodium silicate solution was prepared by dissolving
255.6 grams of Na.sub.2SiO.sub.3.9H.sub.2O and 10 grams of
C.sub.1H.sub.23COOH in 650 grams of water. The sodium aluminate
solution was prepared by dissolving 270.0 grams of NaAlO.sub.2 in
320 grams of water and the sodium hydroxide solution was prepared
by adding 500 grams of NaOH in 650 grams of water. An additional
solution of 10.0 grams of ZnCl.sub.2 and 90.0 grams of water was
also prepared. All solutions were maintained at about 55.degree. C.
after all solids were dissolved. The sodium hydroxide solution was
then added with stirring to the sodium aluminate solution. The
resulting sodium aluminate/sodium hydroxide solution was added
concurrently with the zinc chloride solution to the sodium silicate
solution, again with stirring. The reaction temperature was
maintained at about 60.degree. C. for 2 hours and then filtered and
rinsed.
[0069] A 100 ml Al.sub.2O.sub.3 crucible was heated to 840.degree.
C. in a muffle furnace. The crucible was extracted from the furnace
and a 20.0 gram portion of a dehydrated zeolite prepared according
to Example I was added to the crucible which was then returned to
the furnace and heated for 15 minutes. The heated zeolite powder
was the poured into a stainless steel cup cooled with dry ice
immediately after removal from the furnace. The resulting material
exhibited 0.4% weight gain due to water uptake upon exposure to
ambient conditions after 48 hours. The DTS time of the
TempRite.RTM. 3104 control was increased upon addition of 3 phr of
the shock-annealed zeolite from 14 minutes to 29 minutes (107%
increase over control DTS value). Similarly prepared zeolites were
shock-annealed according to the parameters tabulated below in Table
I:
1TABLE I % H.sub.2O DTS Increase Example Coolant Temperature
(.degree. C.) Time (min) Uptake (%) (min) in DTS 4 Air 840 15 0.8
30.5 118% 5 Air 840 15 1.0 33.6 140% 6 Air 790 20 1.1 28.0 100% 7
Air 830 15 1.1 33.4 139% 8 Air 785 20 1.2 30.5 118% 9 Air 810 15
1.5 33.3 138% 10 CO.sub.2(s) 840 15 0.4 29.4 110% 11 CO.sub.2(s)
820 15 0.8 33.6 140% 12 CO.sub.2(s) 830 15 0.9 33.0 136% 13
CO.sub.2(s) 810 15 1.1 31.9 128% 14 CO.sub.2(s) 820 15 1.5 34.0
143% 15 CO.sub.2(s) 800 15 3.9 31.4 124% 16 CO.sub.2(s) 840 10 4.4
33.3 138% 17 CO.sub.2(s) 790 15 5.7 32.5 132% 18 CO.sub.2(s) 820 10
6.7 31.0 121% 19 CO.sub.2(s) 750 15 8.0 34.0 143% 20 CO.sub.2(s)
770 15 10.5 34.5 146% The (s) subscript in the table with CO.sub.2
indicates that the carbon dioxide was solid. The examples show that
a balance of activity (DTS) and % H.sub.2O uptake can be achieved
with various conditions (temperature, time, cooling
conditions).
EXAMPLES XXI-XXXII
[0070] Another series of zeolite 4A powders were synthesized by
individually preparing the following solutions: (1) a sodium
silicate solution, (2) a sodium aluminate solution; and (3) a
sodium hydroxide solution. The sodium silicate solution was
prepared by dissolving 255.6 grams of Na.sub.2SiO.sub.3.9H.sub.2O
in 650 grams of water. The sodium aluminate solution was prepared
by dissolving 270.0 grams of Na.sub.2AlO.sub.3 in 320 grams of
water, and the sodium hydroxide solution was prepared by adding 500
grams of NaOH in 650 grams of water. All solutions were maintained
at about 55.degree. C. after all the solids were dissolved. An
additional solution of 10.0 grams of ZnCl.sub.2 and 90.0 grams of
water was also prepared and used as shown in the table below. 10
grams of C.sub.11H.sub.23COOH was also added to the sodium silicate
solution as also shown in the table below. The sodium hydroxide
solution was then added with stirring to the sodium aluminate
solution. The resulting sodium aluminate/sodium hydroxide solution
was added concurrently with the zinc chloride solution (when used)
to the sodium silicate solution, again with stirring. The reaction
temperature was maintained at 60.degree. C. for 2 hours and then
filtered and rinsed.
[0071] A 100 mL Al.sub.2O.sub.3 crucible was heated to 840.degree.
C. in a muffle furnace. The crucible was extracted from the furnace
and a 20.0 gram portion of a dehydrated zeolite prepared
accordingly was added to the crucible which was then returned to
the furnace and heated for 15 minutes. The heated zeolite powder
was then poured into a Al.sub.2O.sub.3 crucible at room temperature
and cooled immediately after removal from the furnace. The
resulting material exhibited the weight gain tabulated below due to
water uptake upon exposure to ambient conditions after 48 hours.
The DTS time of the TempRite.RTM. 3104 CPVC control was increased
upon addition to 3 phr of the respective zeolite from 14 minutes to
the value also tabulated below in Table II:
2 TABLE II Particle Size C.sub.11H.sub.23CO mean median % %
H.sub.2O ZnCl.sub.2 OH Shock- diameter diameter <90% DTS
Increase in uptake Example # Added added Annealed (.mu.m) (.mu.m)
(.mu.m) min. DTS (@ 48 hrs.) 21 Yes yes yes 1.4 1.1 2.9 28 100%
0.6% 22 Yes yes no 1.7 1.2 2.5 38 171% 12.3% 23 Yes no yes 1.5 1.1
2.6 27 93% 1.0% 24 Yes no no 1.4 1.1 2.5 35 150% 14.1% 25 No yes
yes 2.1 1.4 5.6 25 79% 0.5% 26 No yes no 1.9 1.6 4.1 32 129% 10.9%
27 No no yes 11.8 6.9 5.6 27 93% 0.8% 28 No no no 27.3 14.9 91.9 30
114% 2.1% 29 Yes yes yes 1.4 1.1 2.2 27 93% 1.0% 30 No no no 1.9
1.5 4.7 31 121% 12.0% 31 Commercial commercial yes 4.3 4.0 7.1 22
57% 2.8% Zeolite zeolite 32 Commercial commercial No 3.9 3.6 6.5 34
143% 16.2% Zeolite zeolite
[0072] This series of experiments was designed to examine the
effects of ZnCl.sub.2, C.sub.11H.sub.23COOH and shock-annealing on
particle size distribution to balance the zeolite reactivity and
H.sub.2O uptake as well as the impact of failing to shock anneal on
the Dynamic Thermal Stability of the compound. The commercial
zeolite used in these examples was molecular sieve zeolite 4A,
having a mean particle size of less than 5 microns, available from
Aldrich and bearing product number 23,366-8 (lot #03024-JQ). In
Example #28, a zeolite was not formed under the noted
conditions.
EXAMPLE XXXIII
[0073] Another zeolite 4A powder was synthesized by individually
preparing the following solutions: sodium silicate, sodium
aluminate and sodium hydroxide solutions. The sodium silicate
solution was prepared by dissolving 195 g of
Na.sub.2SiO.sub.3.5H.sub.2O and 1.5 g. of sodium lauryl sulfate in
525 g. of water. The sodium aluminate solution was prepared by
dissolving 115 g. of NaAlO.sub.2 and 415 g. of water wherein a
solution of NaOH is added comprising 210 g. of NaOH in 420 g. of
water. The resulting sodium aluminate/sodium hydroxide solution was
added to the sodium silicate solution while stirring at room
temperature. A thick gel was instantaneously formed. Agitation was
continued for a couple of minutes until a consistent mixture was
obtained. The system was aged for about 16 hours at room
temperature. After this period of aging, the agitation was started
again and the system was brought to 60.degree. C. The reaction
temperature was maintained for 3 hours. The solution was then
filtered and rinsed.
[0074] The zeolite 4A powder (as confirmed by X-ray diffraction)
has a mean particle diameter of 0.35 .mu.m and <90% value of
0.50 .mu.m as determined using a Coulter LS Particle Size
Analyzer.
[0075] A sample dehydrated at 350.degree. C. exhibited a weight
gain of 22% after 4 days of exposure at ambient conditions. The
dynamic thermal stability (DTS) measured according to ASTM D 2532
in a TempRite.RTM. 3104 CPVC compound (commercially available from
The B. F. Goodrich Company) was evaluated with and without the
above zeolite 4A, using a Brabender torque rheometer set at
208.degree. C. bowl temperature, 35 rpm and a 70 g. loading. The
DTS time of the TempRite.RTM. 3104 CPVC control was 20 minutes.
With the addition of 3 parts per hundred resin (phr) of the zeolite
4A prepared according to this example, to the TempRite.RTM. 3104
compound, the DTS time was increased to 35 minutes, illustrating an
increase of 75% in thermal stability.
EXAMPLE XXXIV
[0076] A commercial zeolite 4A powder (Aldrich product #23,366-8,
(lot #03024 JQ)) has the following particle size distribution as
determined using a Coulter LS Particle Size Analyzer: a mean
particle diameter of 2.5 .mu.m, a median particle diameter of 2.4
.mu.m and a <90% value of 4.6 .mu.m. A sample dehydrated at
350.degree. C. exhibited a weight gain of 21% after 2 days of
exposure to ambient conditions.
[0077] A 100 mL Al.sub.2O.sub.3 crucible was heated to 840.degree.
C. in a muffle furnace. The crucible was extracted from the furnace
and a 20.0 gram portion of the dehydrated commercial zeolite
described above was added to the crucible, which was then returned
to the furnace and heated for 15 minutes. The heated zeolite powder
was then poured into another crucible at room temperature
immediately after removal from the furnace. The resulting material
exhibited 1.0% weight gain due to water uptake upon exposure to
ambient conditions after 48 hours. The DTS time of the
TempRite.RTM. 3104 CPVC control was increased upon addition of 3
phr of the shock-annealed zeolite from 16 minutes to 31.5 minutes
(97% increase in DTS).
EXAMPLE XXXV
[0078] A commercial zeolite 4A powder (Aldrich product #23,366-8,
(lot #03024JQ)) has the following particle size distribution as
determined using a Coulter LS Particle Size Analyzer: a mean
particle size of 2.5 .mu.m, a median particle size of 2.4 .mu.m and
a <90% value of 4.6 .mu.m. A sample dehydrated at 350.degree. C.
exhibited a weight gain of 21% after 2 days of exposure to ambient
conditions.
[0079] A 100 mL Al.sub.2O.sub.3 crucible was heated to 820.degree.
C. in a muffle furnace. The crucible was extracted from the furnace
and a 20.0 gram portion of a dehydrated commercial zeolite
described above was added to the crucible, which was then returned
to the furnace and heated for 15 minutes. The heated zeolite powder
was then poured into a stainless steel cup cooled with dry ice
immediately after removal from the furnace. The resulting material
exhibited 3.2% weight gain due to water uptake upon exposure to
ambient conditions after 48 hours. The DTS time of the
TempRite.RTM. 3104 CPVC control was increased upon addition of 3
phr of the shock-annealed zeolite from 13 minutes to 25 minutes
(92% increase in DTS).
EXAMPLE XXXVI
[0080] TempRite.RTM. 3210 CPVC compound (available from The B. F.
Goodrich Co.) was injection molded using various zeolites as heat
stabilizers.
[0081] Th e zeolite 4A used in this experiment was synthesized in
the laboratory as described previously in Example IV. The zeolite
13X was synthesized in the laboratory as described in U.S. Pat. No.
3,808,321 with the following initial reactant ratios:
H.sub.2O/Na.sub.2O=37.4, Na.sub.2O/SiO.sub.2=1.3,
SiO.sub.2/Al.sub.203=3. The zeolite 13X powder produced (as
determined by X-ray diffraction) has a mean particle size of 1.5
.mu.m and <90% value of 2.1 .mu.m as determined using a Coulter
LS Particle Size Analyzer. Both zeolites were dried in a furnace at
450.degree. C. for 24 hours prior to compounding. The ingredients
were combined into a Banbury mixer until the melt mix temperature
reached 385.degree. F., then the mixture was rolled into sheets
before cubing. Bars were injection molded at 430.degree. F. for
various testing (tensile, impact and heat distortion). The physical
properties as well as a description of the chemical composition and
particle size of the zeolites are summarized in Table III.
[0082] The Congo Red Test was measured in accordance with DIN
Standard 53381, Part 1. The Notched Izod was measured according to
ASTM D 256-93A, the drop impact, and the vice crush according to
ASTM F 441, the tensile tests according to ASTM D 638-95 and the
heat distortion temperature (HDT) according to ASTM D 648-95.
3 TABLE III Compound No. 1a 1b 1c Control- TempRite .RTM. 3210
TempRite .RTM. 3210 TempRite .RTM. 3210 CPVC with CPVC with
Description Compound Zeolite 13X added Zeolite 4A added Amount of
zeolite added 0.0 1.5 1.5 (phr) Mean particle diameter -- 1.5 1.7
(in microns) DTS @ 215 deg C. (min) 10 21 20 Congo Red test (min)
35 52 56 Heat Distortion 104 105 104 Temperature (deg C.) Notched
Izod 2.9 .+-. 0.2 2.0 .+-. 0.4 2.7 .+-. 0.2 (ft.lb./in.) Tensile
Strength (psi) 8320 8370 8560 Tensile Modulus (Kpsi) 340 362 368
Tensile Elongation (%) 15 12 21
[0083] This experiment illustrates that the use of a small particle
size zeolite with reduced water content increases the thermal
stability of a CPVC compound while retaining good physical
properties such as impact, tensile and HDT.
EXAMPLE XXXVII
[0084] A similar experiment was carried out on a commercial high
heat CPVC compound, TempRite.RTM. 3214 CPVC where a small particle
size zeolite 4A containing 8 wt. % of water was used at 2 phr. The
zeolite 4A properties used for the run are described in the
following Table IV (particle size and moisture content). The
zeolite 4A was synthesized as described in Example XXIII and was
shock annealed at 740.degree. C. for 15 min. in exactly the same
manner as described above. Bars were injection molded at
460.degree. F. and physical properties of the molded samples
recorded in Table IV.
4 TABLE IV Compound Control Compound 1 Zeolite Concentration (phr)
0 2 <90% Particle diameter (.mu.m) -- 0.7 Mean particle diameter
(.mu.m) -- 0.47 H.sub.2O Content (%) -- 8.5 Notched Izod (ft.lb/in)
2.2 .+-. 0.2 1.6 .+-. 0.1 Tensile Strength (psi) 8590 .+-. 69 8700
.+-. 43 Tensile Modulus (Kpsi) 396 .+-. 13 407 .+-. 11 Tensile
Elongation (%) 13 13 HDT(.degree. C.) 111 .+-. 2 114 .+-. 3
[0085] This example shows that a CPVC compound containing a small
particle size zeolite with 8 wt. % moisture content will exhibit
poor physical properties due to the outgassing during
processing.
EXAMPLE XXXVIII
[0086] Another experiment was carried out on a commercial high heat
CPVC compound, TempRite.RTM. 3214 CPVC where zeolite 4A was used at
various concentrations. The zeolite 4A characteristics used for
each run are described in the following table (particle size and
moisture content). The zeolites in runs 2b through 2d were
synthesized as described in Example IV and were shock annealed at
840.degree. C. for 15 min. Agglomeration of the individual particle
appears after annealing as indicated by the particles size
distribution in Table V. Run 2e contains a commercial zeolite 4A
from Aldrich which was not dried. Bars were injection molded at
460.degree. F. as described above and physical properties of the
molded samples recorded.
5TABLE V Compound 2a 2b 2c 2d 2e Zeolite 0 1.5 1.5 3 1.5
Concentration (phr) <90% Particle -- 3.2 3.2 3.2 5.7 diameter
(.mu.m) Mean particle -- 1.2 1 1 3.2 diameter (.mu.m) Comments --
Aggregates Aggregates Aggregates Does not at 4 to 8 At 4 to 10 at 4
.mu.m Aggregate .mu.m .mu.m H.sub.2O Content (%) 0.5 0.5 0.5 18%
Notched Izod 1.8 1.2 1.2 0.9 0.8 (ft.lb/in) Tensile Strength (psi)
8640 8800 8940 8960 8950 Tensile Modulus 408 416 426 427 409 (Kpsi)
Tensile Elongation 15 12.7 11.2 12 15 (%) HDT (.degree. C.) 117
.+-. 0 119 .+-. 0 118.5 .+-. 5 120 .+-. 0 117.5 .+-. 5 Congo Red
Test 21.5 40.1 35.4 57.7 43.7 (min.) Visual burned good good Good
surface Appearance (3/4" moisture coupling)
[0087] This example shows that a CPVC compound containing a large
particle size zeolite with no moisture content will exhibit better
thermal stability and processing as compared to the control but
poor physical properties.
EXAMPLE XXXIX
[0088] Physical properties were measured on commercial CPVC
compound TempRite.RTM. 3107 CPVC with the addition of zeolite 4A
synthesized as described in Example XXXIII. The zeolite samples
were dried at 450.degree. C. for 24 hours. The zeolite was coated
with either 33 wt. % butyl tin stabilizer (Mark 292, available from
Witco Chemical) or 37.5 wt % of polydimethylsiloxane oil, (SF100,
available from GE Plastics) under high shear mixing at room
temperature. The polymeric coating was applied to prevent water
reabsorption. The compounds were mixed on a Henschel Mixer at 3600
rpm for 15 min. at 200.degree. F., then rolled into sheets at
400.degree. F. before plaques were pressed. Bars were cut to
measured physical properties as set forth in Table VI.
6 TABLE VI Control 1 2 3 TempRite .RTM. 3107 CPVC 100 100 100 100
(phr) Amount of zeolite added (phr) 0 2 2 2 <90% Zeolite
particle -- 0.6 0.6 0.6 diameter (.mu.m) Zeolite mean particle --
0.4 0.4 0.4 diameter (.mu.m) Coating -- Mark 292 SF100 None 33 wt.
% 37 wt. % % H.sub.2O in Zeolite -- 1.8 1.8 0 Notched Izod 9.5 .+-.
0.8 9.6 .+-. 0.9 10.5 .+-. 0.2 10.2 .+-. 0.5 (ft.lb/in) Tensile
Strength (psi) 7720 .+-. 52 7430 .+-. 18 6650 .+-. 177 7510 .+-. 62
Tensile modulus 335 .+-. 21 355 .+-. 21 337 .+-. 17 338 .+-. 10
(Kpsi) Tensile 5.2 .+-. 0.2 4.7 .+-. 0.1 4.7 .+-. 0.1 5.1 .+-. 0.2
Elongation (%) HDT (.degree. C.) 102 100 108 108
[0089] This example shows that a CPVC compound containing a small
particle zeolite with reduced moisture content will retain good
physical properties as compared to the control.
EXAMPLE XL
[0090] Notched Izod Impact and thermal stability were measured on
commercial CPVC compound 3107 with the addition of a zeolite 4A,
synthesized as described in Example XXXIII, or in the alternative,
commercially available zeolite from Aldrich. The zeolite samples
were dried at 450.degree. C. for 24 hours. Bars were cut to measure
impact properties. The results are summarized in the Table VII.
7 TABLE VII Control 1 2 3 4 5 TempRite .RTM. 3107 100 100 100 100
100 100 CPVC (phr) Amount of zeolite 0 2 2 2 2 2 added (phr)
<90% Zeolite -- 0.6 0.6 4.6 4.6 4.6 particle diameter (.mu.m)
Zeolite mean -- 0.4 0.4 2.5 2.5 2.5 particle diameter (.mu.m)
Coating -- Mark None None SF100 Mark 292 33 wt. % 292 33 wt. % 33
wt. % % H.sub.2O in Zeolite -- 1.8 0 18 2.4 2.4 Notched Izod 6.9
.+-. 0.9 7.4 .+-. 0.5 7.3 .+-. 0.5 2.5 .+-. 0.2 2.7 .+-. 0.1 2.1
.+-. 0.1 (ft.lb.in) DTS (% Increase of -- 55% 55% 55% 95% 66%
Control)
[0091] The DTS increase in Table VII and the application is defined
as (DTS.sub.zeolite containing-DTS.sub.control (no
zeolite)/DTS.sub.control.- times.100%).
[0092] This example shows that a small particle size zeolite with
reduced moisture content is necessary to achieve improved thermal
stabilization than while retaining good impact properties in
CPVC.
EXAMPLE XLI
[0093] Two compounds using Geon 103EPF76 PVC resin from The Geon
Company were made in the following manner. The ingredients were
mixed in a Farrel intensive mixer, removed at 330.degree. F. and
worked on the KSBI 10'.times.20' mill with the front roller set at
420.degree. F. and the back roller set at 400.degree. F. Plaques
were then cut out of the worked material and compression molded to
1/4 in thickness. Bars were then cut from the plaques for Notched
Izod according to ASTM D 256-93A. The remaining compound was cubed
and strips (3 inch wide and 0.035 inches thick) were extruded using
a Brabender {fraction (3/4)} inches diameter single screw extruder
at 195.degree. C. Variable Height Impact Testing (VHIT) was
measured on the strips according to ASTM D 4226. A commercial
zeolite from Aldrich was used in this case and had a large particle
size (as described in the Table VIII) and was shock annealed at
800.degree. C. for 1 hour to prevent any water adsorption.
[0094] The following recipe was used:
8 PVC 103EPF76 100 phr Dibutyl tin bis-(2ethylhexylmercapto
acetate) 2 Titanium dioxide 6 Calcium stearate 1 Acrylic processing
aid 1.5 Impact modifier 6 Shock annealed commercial zeolite 4
[0095]
9 TABLE VIII Control Compound 1 Zeolite content 0 4 <90% Zeolite
Particle -- 5.7 diameter (.mu.m) Mean Particle diameter -- 3.2
(.mu.m) H.sub.2O content (%) -- 0 Izod impact (ft.lb./in.) 2.6 .+-.
0.1 1.8 .+-. 0.4 VHIT impact (in.lb./in.) 2.1 .+-. 0.1 1.85 .+-.
0.1
[0096] This example illustrates that a commercially available
zeolite with reduced water content yields poorer Izod impact and
VHIT impact values in a PVC compound as compared to the
control.
EXAMPLE XLII
[0097] Two compounds using PVC 103EPF76 resin from The Geon Company
were made in the following manner. The ingredients were mixed in an
Henschel mixer at 3600 rpm for 15 min. Strips (2 inches wide and
0.035 inches thick) were extruded at 200.degree. C. via a Haake
conical twin screw extruder at 200.degree. C. The zeolite used in
this case as prepared as described in Example XXXIII and dried in a
furnace at 450.degree. C. before use. Its characteristics are
summarized in the following table. Variable Height Impact Test
(VHIT) values were measured on the strips to quantify impact
properties (ASTM D 4226).
[0098] The following recipe was used:
10 PVC 103EPF76 100 phr Dibutyl tin bis-(2ethylhexylmercapto
acetate) 1.6 Titanium dioxide 1 Calcium stearate 1.5 Paraffin wax
1.5 Oxidized polyethylene 0.1 Acrylic processing aid 1.0 Impact
modifier 5
[0099] The following results were obtained:
11 TABLE IX Control Compound 1 Zeolite content 0 2 <90% Zeolite
Particle diameter (.mu.m) -- 0.6 Mean Particle diameter (.mu.m) --
0.35 H.sub.2O content (%) -- 0 VHIT values (in.lb./in.) 2.43 .+-.
0.18 2.45 .+-. 0.13
[0100] This example illustrates that a small particle size zeolite
with reduced water content yields good impact properties as
illustrated by the VHIT values of the PVC strips.
EXAMPLE XLIII
[0101] 3 phr of a commercial zeolite 4A powder (as received,
Aldrich #23,366-8, lot #03024-JQ) was added to a commercial CPVC
compound (TempRite.RTM. 3104 CPVC). The zeolite had the following
particle size distribution: a mean particle diameter of 2.5 .mu.m,
a median particle diameter of 2.4 .mu.m and a <90% value of 4.6
.mu.m using a Coulter LS Particle Size Analyzer. The same sample
dehydrated at 350.degree. C. exhibited a weight gain of 21% after 2
days of exposure to ambient conditions. The DTS time of the
TempRite.RTM. 3104 CPVC control was increased upon addition of 3
phr of the commercial zeolite from 13 minutes to 33 minutes (154%
increase in DTS). However, staircase drop impact at 22.8.degree. C.
dropped 52% (control: 25 ft.lbs. vs. compound with zeolite 4A: 12
ft.lb.) and hoop stress at 82.2.degree. C. dropped 16% (control:
4900 psi vs. compound with zeolite 4A: 4120 psi) as measured on
extruded 3/4 inch SDR 11 pipe prepared from TempRite.RTM. 3104
CPVC.
EXAMPLE XLIV
[0102] 3 phr of a shock-annealed commercial zeolite 4A powder
(Aldrich zeolite 4A, shock-annealed at 840.degree. C. for 15
minutes) was added to a commercial CPVC compound (TempRite.RTM.
3104 CPVC). The particle size distribution of the shock-annealed
zeolite was determined as follows: a mean particle diameter of 3.1
.mu.m, a median particle diameter of 3.1 .mu.m and a <90% value
of 5.71 .mu.m using a Coulter LS Particle Size Analyzer. The
shock-annealed sample exhibited a weight gain due to water uptake
of <2% after 2 days of exposure to ambient conditions. The DTS
time of the TempRite.RTM. 3104 CPVC control was increased from 16
minutes to 33 minutes (106% increase in DTS). However, the
staircase drop impact at 22.8.degree. C. dropped 44% (control: 25
ft.lb. vs. compound with shock-annealed zeolite: 14 ft.lb.) and
hoop stress at 82.2.degree. C. dropped 9% (control: 4900 psi vs.
compound with shock-annealed zeolite: 4460 psi) as measured on
extruded 3/4 inch SDR 11 pipe prepared from TempRite.RTM. 3104
CPVC.
EXAMPLE XLV
[0103] Polyvinyl chloride was mixed with various additives to
prepare a siding compound, using the following formulation (in
parts by weight)in Table X:
12 TABLE X Material Manufacturer Parts PVC resin (IV = 0.92, Geon
Co. 100.0 Geon 130 EPF 76-TR) Calcium stearate Witco 1.3 Paraffin
wax Witco 1.0 Oxidized polyethylene, Allied Signal 0.1 AC 629
Acrylic process aid, Rohm & Haas 1.25 Paraloid K-120ND Acrylic
toughener Rohm & Haas 6.0 Titanium dioxide, Tioxide 10.0
Tioxide RFC-6 Methyl(thioglycolato) Witco 0.5 to 1.5 tin (IV)-based
stabilizer, Mark 1900 Shock-annealed zeolite Example IV 0.0, 2.0 or
4.0
[0104] The zeolite was synthesized and shock-annealed as outlined
in Example IV. The formulation was well mixed and charged to a
torque rheometer and, run at the following conditions (ASTM D 2532)
set forth in Table XI:
13 TABLE XI Bowl setting (temperature) 170.degree. C. Rotor rate
(RPM) 60 Preheat time 3 min. (at 5-10 rpm) Compound loading 67
grams
[0105] The formulation was continuously mixed at high temperature
until degradation occurred, as evidenced by a substantial change in
torque. Results in Table XII show that the addition of the
shock-annealed zeolite considerably enhanced the stability time
observed for the PVC capstock/unitary construction siding
formulation.
14TABLE XII Shock- Annealed DTS Tin stabilizer Zeolite Time % DTS
Rotor Example (parts) (parts) (min.) Increase conditions A 0.5 0.0
14 0% Clean B 0.5 2.0 24 71% Clean C 0.5 4.0 29 107% Clean D 1.5
0.0 29 0% Clean E 1.5 2.0 43 48% Clean F 1.5 4.0 60 107% Clean
EXAMPLE XLVI
[0106] Polyvinyl chloride was mixed with various additives to
prepare a pipe fittings compound, using the following formulation
(in parts by weight)in Table XIII:
15 TABLE XIII Material Manufacturer Parts PVC resin Geon Co. 100.0
(IV = 0.72) Calcium stearate Witco 0.8 Paraffin wax Witco 0.8
Oxidized polyethylene Allied Signal 0.1 Acrylic process aid Rohm
& Haas 1.0 MBS toughener Rohm & Haas 5.0 Titanium dioxide
Tioxide 1.0 Calcium carbonate Pfizer 3.0
Methyl(thioglycolato)tin(IV- Witco 0.5 or 1.0 based stabilizer
Shock-annealed zeolite Example IV 0.0, 2.0 or 4.0 (Example IV)
[0107] The zeolite was synthesized and shock-annealed as described
in Example IV. The formulation was well mixed and charged to a
torque rheometer, run at the following conditions (ASTM D 2532) in
Table XIV:
16 TABLE XIV Bowl setting (temperature) 170.degree. C. Rotor rate
(RPM) 60 Preheat time 3 min. (at 5-10 RPM) Compound loading 67
grams
[0108] The formulation was continuously mixed at high temperature
until degradation occurred, as evidenced by a substantial change in
torque. Results in Table XV showed that the addition of the
shock-annealed zeolite considerably enhanced the stability time
observed for the PVC fitting formulation.
17TABLE XV Shock- Annealed DTS Tin stabilizer Zeolite Time % DTS
Rotor Example (parts) (parts) (min.) Increase conditions G 0.5 0.0
17 0% Sticking H 0.5 2.0 20 18% Clean I 0.5 4.0 22 29% Clean J 1.0
0.0 24 0% Sticking K 1.0 2.0 25 4% Clean L 1.0 4.0 31 29% Clean
EXAMPLE XLVII
[0109] 1 inch schedule 40 pipe extrusion was carried out using a
CM-55 HP twin screw extruder with a commercial TempRite.RTM. 3104
CPVC compound using 3 parts of commercial zeolite from Aldrich
which had an average particle diameter of 3.1 .mu.m and a 90% and
below value of 5.7 .mu.m. The zeolite was dried at 450.degree. C.
for 24 hours prior to compounding. A counterrotating intermeshing
twin screw extruder, CM55HP, manufactured by Cincinnati Milacron
was used to extrude the pipe. The extruder was run at 420.degree.
F. with a screw rotation speed of 20 rpm in this Example. The
results of the physical properties of the extruded sample (pipe
properties) are as follows in Table XVI:
18 TABLE XVI Control 1 2 TempRite .RTM. 3104 CPVC 100 100 100
Zeolite 4A -- 3 3 % DTS increase 118% 118% Staircase Drop Impact at
40 .+-. 3 11 .+-. 1 20 .+-. 4 73.degree. F. (ft.lb) Staircase Drop
10 + 1 <6 <6 Impact at 32.degree. F. (ft.lb) Vice Crush
passes 3/3 3/3 3/3 Compression 60% full 3/3 2/3 3/3 Pipe Appearance
Good Very poor Poor (pimples)
[0110] In this extrusion run, while the thermal stability is
increased by the presence of the commercial zeolite, it also
reduces the staircase drop impact by 50 to 80% at 73.degree. F. and
over 40% at 32.degree. F.; the vice crush test is substantially
equivalent in the absence or presence of the zeolite and the pipe
appearance is poorer when the large particles size zeolite is used
(pimples).
EXAMPLE XLVIII
[0111] Two compounds were formulated using the 69.7% chlorine
two-step CPVC Resin formed described in U.S. Pat. No. 5,216,088.
These resins were formulated into compounds using the 69.5%
chlorine recipe set forth in Table 3 of European Patent Application
EP 808851 A2 with the following modifications: 69.7% chlorine
two-step CPVC resin and 3 parts of chlorinated polyethylene were
used in this Example as well as 0.25 parts of antioxidant along
with commercial Linde 13X zeolite which had been pre-dried for 54
hours at 286.degree. C. followed by cooling under vacuum were made
in the following manner. Zeolite 13X had a average particle size of
about 5.5 microns and was immediately used to minimize water
absorption. The ingredients were mixed in the Farrell intensive
mixer, removed at 420.degree. C. and worked on the KSBI
10'.times.20' mill with the front roller set at 430.degree. F. and
the back rollers at 420.degree. F. Plaques were then cut out of the
worked material and compression molded to 1/8 inch and 1/4 inch
thickness using the following Wabash press conditions:
19 Pressure setting 50 tons Pressure Temperature 410.degree. C. Low
pressure 6 minutes High pressure 3 minutes Pre-bump dwell 15
seconds Dwell between bumps 5 seconds Bump open time 8 seconds Bump
counter 2
[0112] Bars were cut from the final plaques for Notched Izod
according to ASTM D 256-93A, and tensile strength according to ASTM
D 638-94B. The results are summarized in Table XVII below:
20 TABLE XVII Compound with Control Zeolite 13X added 1/4" Notched
Izod, 23.degree. C. 1.77 0.72 (ft.lb./in.) 1/8" Tensile Strength,
23.degree. C. 7810 7460 (psi) DTS-210.degree. C. DTS Min. 2330 2330
35 rpm, 82 gm Torque cubes (m-gm) DTS Min. 6.4 12.8 Time (minutes)
DTS Temp. 231 233 (.degree. C.)
[0113] This example shows that commercially available zeolite that
has been dried increases the thermal stability time as evidenced by
the longer DTS time but yield poorer Izod impact values as a result
of large particle size.
EXAMPLE XLIX
[0114] Polyvinyl chloride was mixed with various additives to
prepare a compound, using the following formulation (in parts by
weight) in Table XVIII:
21 TABLE XVIII Material Manufacturer Parts PVC resin G27LIV Geon
Co. 100.0 (IV = 0.92) Calcium stearate Witco 1.5 Paraffin wax Witco
1.5 Oxidized polyethylene Allied Signal 0.1 Acrylic process aid
Robin & Haas 1.0 Acrylic toughener Robin & Haas 3.5
Titanium dioxide Tioxide 1.0 Calcium carbonate Pfizer 8.0
Methyl(thioglycolato)tin(IV)- Witco 0.5 to 1.5 based stabilizer
Zeolite 4A Example XXXIII 0.0 to 0.75
[0115] The zeolite was synthesized as described in Example XXXIII.
The formulation was well mixed and charged to a torque rheometer,
run at the following conditions (ASTM D 2532) in Table XIX:
22 TABLE XIX Bowl setting (temperature) 200.degree. C. Rotor rate
(RPM) 66 Preheat time 3 min. (at 5-10 RPM) Compound loading 68
grams
[0116] The formulation was continuously mixed at high temperature
until degradation occurred, as evidenced by a substantial change in
torque. Results in Table XX showed that the combination of the
zeolite with reduced level of tin glycolate stabilizer demonstrated
a similar or better thermal stability time than the PVC formulation
containing a large amount of tin stabilizer without zeolite, which
indicates synergic activity between the tin stabilizer and the
zeolite.
23 TABLE XX Tin Stabilizer Zeolite DTS time Example (parts) (parts)
(min.) M 1.5 0.0 8.8 N 0.75 0.5 11.3 O 0.75 0.25 9.4 P 0.5 0.75
10.6 Q 0.5 0.5 9.1
EXAMPLE L
[0117] Chlorinated polyvinyl chloride (0.92 IV, 67%Cl) was mixed
with various additives to prepare a compound, using the following
formulation (in parts by weight) in Table XXII:
24 TABLE XXII Material Parts CPVC resin (IV = 0.92, 67% Cl) 100.0
Paraffin wax 1.0 Oxidized polyethylene 1.3 MABS toughener 7.0
Titanium dioxide 4.0 Processing aid 2.0 Dibutyl tin bis-lauryl
maleate 1.2 to 2.4 Zeolite 4A (example XXXIII) 0.0 to 0.5
[0118] The formulation was well mixed and charged to a torque
rheometer and run at the following conditions (ASTM D 2532) in
Table XXIII:
25 TABLE XXIII Bowl setting (temperature) 206.degree. C. Rotor rate
(RPM) 35 Preheat time 3 min. (at 5-10 RPM) Compound loading 70
grams
[0119] The zeolite was synthesized as described in Example XXXIII.
The formulation was continuously mixed at high temperature until
degradation occurred, as evidenced by a substantial change in
torque. Results in Table XXIV showed that the combination of the
zeolite with reduced level of tin maleate stabilizer demonstrated a
similar or better thermal stability time than the CPVC formulation
containing a large amount of tin maleate stabilizer without
zeolite, which indicates synergic activity between the tin
stabilizer and the zeolite.
26 TABLE XXIV Tin Stabilizer Zeolite DTS time Example (parts)
(parts) (min.) R 2.4 0.0 13.5 S 1.2 0.5 16.8
[0120] In summary, novel and unobvious halogen containing polymer
compounds with a modified zeolite stabilizer have been described.
Although specific embodiments and examples have been disclosed
herein, it should be borne in mind that these have been provided by
way of explanation and illustration and the present invention is
not limited thereby. Certainly modifications which are within the
ordinary skill in the art are considered to lie within the scope of
this invention as defined by the following claims.
* * * * *