U.S. patent application number 16/385918 was filed with the patent office on 2019-10-17 for bio-based elastomeric eva compositions and articles and methods thereof.
This patent application is currently assigned to Braskem S.A.. The applicant listed for this patent is Braskem S.A.. Invention is credited to Giancarlos Delevati, Jose Augusto Esteves Viveiro, Fernanda Munhoz Anderle, Omar Wandir Renck, Mauro Alfredo Soto Oviedo.
Application Number | 20190315949 16/385918 |
Document ID | / |
Family ID | 68161302 |
Filed Date | 2019-10-17 |
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United States Patent
Application |
20190315949 |
Kind Code |
A1 |
Delevati; Giancarlos ; et
al. |
October 17, 2019 |
BIO-BASED ELASTOMERIC EVA COMPOSITIONS AND ARTICLES AND METHODS
THEREOF
Abstract
A polymer composition may include an elastomeric ethylene-vinyl
acetate, in which at least a portion of ethylene from the
elastomeric ethylene-vinyl acetate is obtained from a renewable
source of carbon. A curable polymer composition, an expandable
polymer composition, articles, cured articles, and expanded
articles may include or be formed from such polymer composition. A
process for producing a polymer composition may include
polymerizing ethylene at least partially obtained from a renewable
source of carbon with vinyl acetate to produce an ethylene vinyl
acetate copolymer; and mixing the ethylene-vinyl acetate copolymer
with an elastomeric polyolefin to produce an elastomeric
ethylene-vinyl acetate.
Inventors: |
Delevati; Giancarlos; (Sao
Paulo, BR) ; Soto Oviedo; Mauro Alfredo; (Sao Paulo,
BR) ; Munhoz Anderle; Fernanda; (Sao Paulo, BR)
; Renck; Omar Wandir; (Sao Paulo, BR) ; Esteves
Viveiro; Jose Augusto; (Sao Paulo, BR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Braskem S.A. |
Camacari |
|
BR |
|
|
Assignee: |
Braskem S.A.
Camacari
BR
|
Family ID: |
68161302 |
Appl. No.: |
16/385918 |
Filed: |
April 16, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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PCT/IB2019/020007 |
Apr 12, 2019 |
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16385918 |
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62658283 |
Apr 16, 2018 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 77/04 20130101;
C08L 2203/14 20130101; C08L 23/0807 20130101; C08K 5/14 20130101;
C08L 2205/025 20130101; C08K 2003/265 20130101; C08K 2003/2296
20130101; C08L 83/04 20130101; C08L 23/0853 20130101; C08K 5/0016
20130101; C08K 5/16 20130101; C08K 5/14 20130101; C08L 23/0853
20130101; C08L 23/0853 20130101; C08L 23/0853 20130101; C08K
2003/265 20130101; C08K 2003/2296 20130101; C08K 5/14 20130101;
C08K 5/16 20130101 |
International
Class: |
C08L 23/08 20060101
C08L023/08 |
Claims
1. A polymer composition, comprising: an elastomeric ethylene-vinyl
acetate, in which at least a portion of ethylene from the
elastomeric ethylene-vinyl acetate is obtained from a renewable
source of carbon.
2. The polymer composition of claim 1, wherein the elastomeric
ethylene-vinyl acetate comprises: an ethylene vinyl acetate
copolymer; an ethylene alpha-olefin copolymer; and a rubber.
3. The polymer composition of claim 2, wherein the elastomeric
ethylene-vinyl acetate comprises: the ethylene vinyl acetate
copolymer at a percent by weight in the range of 20 wt % to 90 wt
%; the ethylene alpha-olefin copolymer at a percent by weight in
the range of 5% to 60%; the rubber at a percent by weight in the
range of 0.5 wt % to 40 wt %; a polyorganosiloxane at a percent by
weight in the range of 0.1 wt % to 10 wt %; and a plasticizer at a
percent by weight in the range of 0.5 wt % to 20 wt %.
4. The polymer composition of claim 2, wherein the ethylene
alpha-olefin copolymer is prepared from a C3 to C20 alpha-olefin
monomer.
5. The polymer composition of claim 1, wherein the vinyl acetate is
at least partially obtained from a renewable source of carbon.
6. The polymer composition of claim 1, wherein the vinyl acetate is
present in the copolymer in an amount ranging from 5 to 40 wt
%.
7. The polymer composition of claim 1, wherein the ethylene is
present in the copolymer in an amount ranging from 60 to 95 wt
%.
8. The polymer composition of claim 1, wherein the polymer
composition exhibits a biobased carbon content as determined by
ASTM D6866-18 Method B of at least 5%.
9. An article prepared from the polymer composition of claim 1.
10. A curable polymer composition comprising the polymer
composition of claim 1 and at least a peroxide agent.
11. A cured non-expanded article prepared from the curable polymer
composition of claim 10.
12. The cured non-expanded article of claim 11, wherein the cured
article exhibits a density as determined by ASTM D-792 within the
range of 0.7 to 1.2 g/cm3.
13. The cured non-expanded article of claim 11, wherein the cured
article exhibits a Shore A hardness as determined by ASTM D2240 in
the range of 40 to 90 Shore A.
14. The cured non-expanded article of claim 11, wherein the cured
article exhibits an abrasion resistance, as determined by ISO
4649:2017 measured with a load of 10N, within the range 10 mm.sup.3
to 250 mm.sup.3.
15. The cured non-expanded article of claim 11, wherein the cured
article exhibits an elongation at break as determined by ASTM D638
of at least 200%.
16. The cured non-expanded article of claim 11, wherein the cured
article exhibits a biobased carbon content, as determined by ASTM
D6866-18 Method B, of at least 5%.
17. An expandable polymer composition comprising the polymer
composition of claim 1 and at least a blowing agent and a peroxide
agent.
18. An expanded article prepared from the expandable polymer
composition of claim 17.
19. The expanded article of claim 18, wherein the expanded article
exhibits a density as determined by ASTM D-792 within the range of
0.05 to 0.9 g/cm.sup.3.
20. The expanded article of claim 18, wherein the expanded article
exhibits an Asker C hardness as determined by ABNT NBR 14455:2015
in the range of 20 to 95 Asker C.
21. The expanded article of claim 18, wherein the expanded article
exhibits a permanent compression set as determined by ASTM
D395:2016 Method B in the range of 20% to 100%.
22. The expanded article of claim 18, wherein the expanded article
exhibits a rebound as determined by ABNT NBR 8619:2015 within the
range of 30% to 80%.
23. The expanded article of claim 18, wherein the expanded article
exhibits an abrasion resistance as determined by ISO 4649 measured
with a load of 5N within the range 40 mm.sup.3 to 700 mm.sup.3.
24. The expanded article of claim 18, wherein the expanded article
exhibits a shrinkage as determined at 70.degree. C.*1 h according
to the PFI method between 0.1 and 7%.
25. The expanded article of claim 18, wherein the expanded article
exhibits an elongation at break as determined by ASTM D638 of at
least 300%.
26. The expanded article of claim 18, wherein the expanded article
exhibits a biobased carbon content as determined by ASTM D6866-18
Method B of at least 5%.
27. The article of claim 9, wherein the article is selected from a
group consisting of shoe soles, midsoles, outsoles, unisoles,
insoles, monobloc sandals, flip flops, full EVA footwear, sportive
articles, seals, hoses, gaskets, foams, foam mattresses and
automotive parts.
28. A process for producing a polymer composition, comprising:
polymerizing ethylene at least partially obtained from a renewable
source of carbon with vinyl acetate to produce an ethylene vinyl
acetate copolymer; and mixing the ethylene-vinyl acetate copolymer
with an elastomeric polyolefin to produce an elastomeric
ethylene-vinyl acetate.
29. The process of claim 28, wherein the elastomeric polyolefin
comprises an ethylene alpha-olefin copolymer and rubber.
30. The process of claim 28, wherein the mixing comprises mixing:
the EVA copolymer at a percent by weight in the range of 20 wt % to
90 wt %; an ethylene alpha-olefin copolymer at a percent by weight
in the range of 5% to 60%; a polyorganosiloxane at a percent by
weight in the range of 0.1 wt % to 10 wt %; a plasticizer at a
percent by weight in the range of 0.5 wt % to 20 wt %; and a rubber
at a percent by weight in the range of 0.5 wt % to 40 wt %.
31. The process of claim 28, wherein the polymer composition
exhibits a biobased carbon content as determined by ASTM D6866-18
Method B of at least 5%.
32. The process of claim 28, wherein the vinyl acetate is at least
partially obtained from a renewable source of carbon.
33. The process of claim 28, further comprising: fermenting a
renewable source of carbon to produce ethanol; and dehydrating the
ethanol to produce ethylene.
34. The process of claim 33, wherein the fermenting produces the
ethanol and a mixture of byproducts comprising higher alcohols, and
the dehydration produces ethylene and higher alkene impurities,
wherein the process further comprises: purifying the ethylene and
higher alkene impurities in order to obtain the ethylene.
35. The process of claim 33, wherein the fermenting produces the
ethanol and byproducts comprising higher alcohols, wherein the
process further comprises: purifying the ethanol and byproducts in
order to obtain the ethanol.
36. The process of claim 33, wherein the renewable source of carbon
is at least one plant material selected from the group consisting
of sugar cane and sugar beet, maple, date palm, sugar palm,
sorghum, American agave, corn, wheat, barley, sorghum, rice,
potato, cassava, sweet potato, algae, fruit, materials comprising
cellulose, wine, materials comprising hemicelluloses, materials
comprising lignin, wood, straw, sugarcane bagasse, sugarcane
leaves, corn stover, wood residues, paper, and combinations
thereof.
37. The process of any of claim 28, wherein the process further
comprises: curing the polymer composition in the presence of a
peroxide agent.
38. The process of any of claim 28, wherein the process further
comprises: curing and expanding the polymer composition in the
presence of at least a blowing agent and a peroxide agent.
39. The process of claim 38, wherein the curing of the polymer
composition occurs in a full or partial presence of oxygen.
Description
BACKGROUND
[0001] Commercial rubber compositions may be formulated with a
variety of primary and secondary polymers and various additives to
tune performance based on the final application. For example,
rubber compositions that are normally used in the footwear market
require a large number of raw materials in order to achieve the
attributes necessary for the application, leading to the production
of complex and specialized mixtures.
[0002] In addition to complex formulations containing a number of
additives, curing and vulcanization may create further constraints,
limiting the ability to change formulations or reuse rubbers for
different applications. The processing difficulty with traditional
rubber bases such as SBR (styrene-butadiene rubber), natural rubber
and/or blends of different synthetic or natural rubbers, has
motivated the search for alternative base materials having similar
or improved properties, such as low abrasion, soft touch and
lightness, and a reduced number of formulation components
SUMMARY
[0003] This summary is provided to introduce a selection of
concepts that are further described below in the detailed
description. This summary is not intended to identify key or
essential features of the claimed subject matter, nor is it
intended to be used as an aid in limiting the scope of the claimed
subject matter.
[0004] In one aspect, embodiments disclosed herein relate to a
polymer composition that includes an elastomeric ethylene-vinyl
acetate, in which at least a portion of ethylene from the
elastomeric ethylene-vinyl acetate is obtained from a renewable
source of carbon.
[0005] In another aspect, embodiments disclosed herein relate to an
article that may be prepared from a polymer composition that
includes an elastomeric ethylene-vinyl acetate, in which at least a
portion of ethylene from the elastomeric ethylene-vinyl acetate is
obtained from a renewable source of carbon.
[0006] In another aspect, embodiments disclosed herein relate to a
curable a polymer composition that includes an elastomeric
ethylene-vinyl acetate, in which at least a portion of ethylene
from the elastomeric ethylene-vinyl acetate is obtained from a
renewable source of carbon, and at least a peroxide agent.
[0007] In yet another aspect, embodiments disclosed herein relate
to a cured article prepared from the curable polymer composition
that includes an elastomeric ethylene-vinyl acetate, in which at
least a portion of ethylene from the elastomeric ethylene-vinyl
acetate is obtained from a renewable source of carbon, and at least
a peroxide agent.
[0008] In another aspect, embodiments disclosed herein relate to an
expandable polymer composition that includes an elastomeric
ethylene-vinyl acetate, in which at least a portion of ethylene
from the elastomeric ethylene-vinyl acetate is obtained from a
renewable source of carbon, and at least a blowing agent and a
peroxide agent.
[0009] In another aspect, embodiments disclosed herein relate to an
expanded article prepared from the expandable polymer composition
that includes an elastomeric ethylene-vinyl acetate, in which at
least a portion of ethylene from the elastomeric ethylene-vinyl
acetate is obtained from a renewable source of carbon, and at least
a blowing agent and a peroxide agent.
[0010] In yet another aspect, embodiments disclosed herein relate
to a process for producing a polymer composition that includes
polymerizing ethylene at least partially obtained from a renewable
source of carbon with vinyl acetate to produce an ethylene vinyl
acetate copolymer; and mixing the ethylene-vinyl acetate copolymer
with an elastomeric polyolefin to produce an elastomeric
ethylene-vinyl acetate.
[0011] In yet another aspect, embodiments disclosed herein relate
to a process for producing a polymer composition that includes
fermenting a renewable source of carbon to produce ethanol;
dehydration of ethanol to produce ethylene; polymerizing ethylene
and vinyl acetate to produce an ethylene vinyl acetate copolymer;
and mixing the ethylene-vinyl acetate copolymer with an elastomeric
polyolefin to produce an elastomeric ethylene-vinyl acetate.
[0012] Other aspects and advantages of the claimed subject matter
will be apparent from the following description and the appended
claims.
BRIEF DESCRIPTION OF DRAWINGS
[0013] FIG. 1 is an exemplary route for the production of bio-based
vinyl acetate according to one or more embodiments of the present
disclosure.
[0014] FIG. 2 depicts various points pertinent to the PFI method of
determining article shrinkage according to one or more embodiments
of the present disclosure.
DETAILED DESCRIPTION
[0015] In one aspect, embodiments disclosed herein relate to rubber
compositions containing elastomeric ethylene vinyl acetate (EVA)
copolymers that have at least a portion of the ethylene thereof
that is obtained from a renewable source of carbon, such as a
plant-based material, i.e., forming a bio-based elastomeric
ethylene vinyl acetate copolymer.
[0016] Polymer compositions in accordance with the present
disclosure may be used for the partial or total replacement of
rubbers such as styrene-butadiene rubber to prepare expanded and
non-expanded articles in applications including shoe sole
components, monobloc expanded soles for sandals or flip-flops, and
the like, while retaining the required technical requirements
demanded by these applications.
[0017] Polymer compositions in accordance with the present
disclosure may include the reaction products obtained from a
mixture of: an elastomeric EVA composition; and one or more of
filler, blowing agent, curing agent, or blowing accelerator. The
elastomeric EVA may include, for example, a bio-based ethylene
vinyl acetate copolymer, an ethylene-alpha olefin copolymer and
rubber. Each of the components are discussed in turn as follows
[0018] EVA is a copolymer of the polyolefin family of elastomers
formed by the sequence of random units derived from the
polymerization of ethylene and vinyl acetate at high temperature
and pressure. EVA copolymers provide materials that can be
processed like other thermoplastics, but may offer a rubbery
character having softness and elasticity. The use of products
derived from natural sources, as opposed to those obtained from
fossil sources, has increasingly been widely preferred alternative,
as an effective means of reducing the atmospheric carbon dioxide
concentration increase, therefore effectively limiting the
expansion of the greenhouse effect. Products obtained from natural
raw materials have a difference, relative to fossil sourced
products, in their renewable carbon content. This renewable carbon
content can be certified by the methodology described in the
technical ASTM D 6866-18 Norm, "Standard Test Methods for
Determining the Biobased Content of Solid, Liquid, and Gaseous
Samples Using Radiocarbon Analysis". Products obtained from
renewable natural raw materials have the additional property of
being able to be incinerated at the end of their life cycle and
only produce CO.sub.2 of a non-fossil origin. Further, while
particular embodiments of the present disclosure may be directed to
use of bio-based EVA copolymers in the production of the
elastomeric EVA compositions, it is also understood that one or
more other components may also be formed from renewable sources.
Thus, while some of the below discussion is directed to the amount
of bio-based carbon in an EVA copolymer, in one or more
embodiments, the elastomeric EVA composition may exhibit a
bio-based carbon content, as determined by ASTM D6866-18 Method B
of at least 5%. Further, other embodiments may include at least
10%, 20%, 40%, 50%, 60%, 80%, or 90% bio-based carbon. Such
bio-based carbon may be entirely contributed by the EVA copolymer
or may also be contributed by other components as well.
[0019] Elastomeric EVA Composition
[0020] Polymeric compositions in accordance with one or more
embodiments of the present disclosure may include an elastomeric
ethylene vinyl acetate (EVA) composition may be prepared from of
(A) a bio-based EVA copolymer, (B) ethylene alpha-olefin copolymer,
(C) polyorganosiloxane, (D) plasticizer, and (E) rubber, that are
crosslinked in some embodiments by a (F) crosslinking agent.
Elastomeric EVA compositions are prepared as disclosed in the
Brazilian patent BR102012025160-4, and U.S. Patent Application No.
62/594,307, both of which are incorporated herein in their
entirety. The major components of the elastomer composition of the
present disclosure as well as their respective properties are
detailed below.
[0021] (A) EVA Copolymer
[0022] Elastomeric EVA compositions in accordance may incorporate
one or more ethylene-vinyl acetate (EVA) copolymers prepared by the
copolymerization of ethylene and vinyl acetate. In some
embodiments, the EVA copolymer can be derived from fossil or
renewable sources such as biobased EVA. Biobased EVA is an EVA
wherein at least one of ethylene and/or vinyl acetate monomers are
derived from renewable sources, such as ethylene derived from
biobased ethanol.
[0023] Polymer compositions in accordance with the present
disclosure may include an EVA copolymer, wherein the percent by
weight of ethylene in the EVA polymer ranges from a lower limit
selected from one of 60 wt %, 66 wt %, and 72 wt %, to an upper
limit selected from one of 82 wt %, 88 wt %, 92 wt %, and 95wt %,
where any lower limit may be paired with any upper limit. Further,
of this total amount of ethylene, it is understood that at least a
portion of that ethylene is based on a renewable carbon source.
[0024] Polymer compositions in accordance with the present
disclosure may include EVA copolymers incorporating various ratios
of ethylene and vinyl acetate. Polymer compositions in accordance
with the present disclosure may include an EVA copolymer, wherein
the percent by weight of vinyl acetate in the copolymer, as
determined by ASTM D5594, ranges from a lower limit selected from
one of 5 wt %, 8 wt %, 12 wt %, and 18 wt % to an upper limit
selected from 28 wt %, 33 wt %, and 40 wt %, where any lower limit
may be paired with any upper limit. Further, of this total amount
of vinyl acetate, it is understood that at least a portion of that
vinyl acetate is based on a renewable carbon source.
[0025] Specifically, in one or more embodiments, the EVA copolymer
exhibits a bio-based carbon content, as determined by ASTM D6866-18
Method B of at least 5%. Further, other embodiments may include at
least 10%, 20%, 40%, 50%, 60%, 80%, or 100% bio-based carbon. As
mentioned above, the total bio-based or renewable carbon in the EVA
polymer may be contributed from a bio-based ethylene and/or a
bio-based vinyl acetate. Each of these are described in turn.
[0026] For example, in one or more embodiments, the renewable
source of carbon is one or more plant materials selected from the
group consisting of sugar cane and sugar beet, maple, date palm,
sugar palm, sorghum, American agave, corn, wheat, barley, sorghum,
rice, potato, cassava, sweet potato, algae, fruit, materials
comprising cellulose, wine, materials comprising hemicelluloses,
materials comprising lignin, wood, straw, sugarcane bagasse,
sugarcane leaves, corn stover, wood residues, paper, and
combinations thereof.
[0027] In one or more embodiments, the bio-based ethylene may be
obtained by fermenting a renewable source of carbon to produce
ethanol, which may be subsequently dehydrated to produce ethylene.
Further, it is also understood that the fermenting produces, in
addition to the ethanol, byproducts of higher alcohols. If the
higher alcohol byproducts are present during the dehydration, then
higher alkene impurities may be formed alongside the ethanol. Thus,
in one or more embodiments, the ethanol may be purified prior to
dehydration to remove the higher alcohol byproducts while in other
embodiments, the ethylene may be purified to remove the higher
alkene impurities after dehydration.
[0028] Thus, biologically sourced ethanol, known as bio-ethanol, is
obtained by the fermentation of sugars derived from cultures such
as that of sugar cane and beets, or from hydrolyzed starch, which
is, in turn, associated with other cultures such as corn. It is
also envisioned that the bio-based ethylene may be obtained from
hydrolysis based products from cellulose and hemi-cellulose, which
can be found in many agricultural by-products, such as straw and
sugar cane husks. This fermentation is carried out in the presence
of varied microorganisms, the most important of such being the
yeast Saccharomyces cerevisiae. The ethanol resulting therefrom may
be converted into ethylene by means of a catalytic reaction at
temperatures usually above 300.degree. C. A large variety of
catalysts can be used for this purpose, such as high specific
surface area gamma-alumina. Other examples include the teachings
described in U.S. Pat. Nos. 9,181,143 and 4,396,789, which are
herein incorporated by reference in their entirety.
[0029] Bio-based vinyl acetate, on the other hand, may also be used
in one of more embodiments of the EVA copolymer of the present
disclosure. Bio-based vinyl acetate may be produced by producing
acetic acid by oxidation of ethanol (which may be formed as
described above) followed by reaction of ethylene and acetic acid
to acyloxylate the ethylene and arrive at vinyl acetate. Further,
it is understood that the ethylene reacted with the acetic acid may
also be formed from a renewable source as described above.
[0030] An exemplary route of obtaining a bio-based vinyl acetate is
shown in FIG. 1. As shown, initially, a fermentation of a renewable
starting material, including those described above, and optional
purification, in order to produce at least one alcohol (either
ethanol or a mixture of alcohols including ethanol). The alcohol
may be separated into two parts, where the first part is introduced
into a first reactor and the second part may be introduced into a
second reactor. In the first reactor, the alcohol may be dehydrated
in order to produce an alkene (ethylene or a mixture of alkenes
including ethylene, depending on whether a purification followed
the fermentation) followed by optional purification to obtain
ethylene. One of ordinary skill in the art may appreciate that if
the purification occurs prior to dehydration, then it need not
occur after dehydration, and vice versa. In the second reactor, the
alcohol may be oxidized in order to obtain acetic acid, which may
optionally be purified. In a third reactor, the ethylene produced
in the first reactor and the acetic acid produced in the second
reactor may be combined and reacted to acyloxylate the ethylene and
form vinyl acetate, which may be subsequently isolated and
optionally purified. Additional details about oxidation of ethanol
to form acetic acid may be found in U.S. Pat. No. 5,840,971 and
Selective catalytic oxidation of ethanol to acetic acid on
dispersed Mo--V--Nb mixed oxides. Li X, Iglesia E. Chemistry. 2007;
13(33):9324-30.
[0031] However, the present disclosure is not so limited in terms
of the route of forming acetic acid. Rather, it is also envisioned,
as indicated on FIG. 1, that acetic acid may be obtained from a
fatty acid, as described in The Production of Vinyl Acetate Monomer
as a Co-Product from the Non-Catalytic Cracking of Soybean Oil,
Benjamin Jones, Michael Linnen, Brian Tande and Wayne Seames,
Processes, 2015, 3, 61-9-633. Further, the production of acetic
acid from fermentation performed by acetogenic bacteria, as
described in Acetic acid bacteria: A group of bacteria with
versatile biotechnological applications, Saichana N, Matsushita K,
Adachi O, Frebort I, Frebortova J. Biotechnol Adv. 2015 Nov. 1;
33(6 Pt 2):1260-71 and Biotechnological applications of acetic acid
bacteria. Raspor P, Goranovic D. Crit Rev Biotechnol. 2008;
28(2):101-24. Further, it is also understood that while FIG. 1 is
directed to the formation of vinyl acetate, the production of
ethylene used to produce vinyl acetate can also be used to form the
ethylene that is subsequently reacted with the vinyl acetate to
form the EVA copolymer of the present disclosure. Thus, for
example, the amount of ethanol that is fed to the first and second
reactors, respectively, may be vary depending on the relative
amounts of ethylene and vinyl acetate being polymerized.
[0032] Polymer compositions in accordance with the present
disclosure may include an EVA copolymer, wherein the number average
molecular weight (Mn) in kilodaltons (kDa) of the EVA copolymer
ranges from a lower limit selected from one of 5 kDa, 10 kDa, 20
kDa and 25 kDa to an upper limit selected from one of 30 kDa, 35
kDa, 40 kDa and 50 kDa, where any lower limit may be paired with
any upper limit.
[0033] Polymer compositions in accordance with the present
disclosure may include an EVA copolymer, wherein the weight average
molecular weight (Mw) in kilodaltons (kDa) of the EVA copolymer
ranges from a lower limit selected from one of 25 kDa, 50 kDa, 70
kDa, 90 kDa and 110 kDa to an upper limit selected from one of 120
kDa, 140 kDa, 150 kDa and 180 kDa, where any lower limit may be
paired with any upper limit.
[0034] Polymer compositions in accordance with the present
disclosure may include an EVA copolymer, wherein the dispersity
(Mw/Mn) of the EVA copolymer ranges from a lower limit selected
from one of 1.0, 1.5, 3.0 and 4.0 to an upper limit selected from
one of 5.0, 6.0, 7.0 and 8.0, where any lower limit may be paired
with any upper limit.
[0035] The molecular weight properties may be measured by GPC (Gel
Permeation Chromatography) experiments. Such experiments may be
coupled with triple detection, such as with an infrared detector
IRS and a four-bridge capillary viscometer (Polymer Char) and an
eight-angle light scattering detector (Wyatt). A set of 4 mixed
bed, 13 .mu.m columns (Tosoh) may be used at a temperature of
140.degree. C. The experiments may use a concentration of 1 mg/mL,
a flow rate of 1 mL/min, a dissolution temperature and time of
160.degree. C. and 90 minutes, respectively, an injection volume of
200 .mu.L, and a solvent of trichlorium benzene stabilized with 100
ppm of BHT.
[0036] Elastomeric EVA compositions in accordance with the present
disclosure may contain an ethylene vinyl acetate copolymer at a
percent by weight (wt %) of the composition that ranges from a
lower limit of 20 wt %, 30 wt %, 40 wt %, or 50 wt %, to an upper
limit of 60 wt %, 70 wt %, 80 wt %, or 90 wt %, where any lower
limit may be paired with any upper limit.
[0037] (B) Ethylene Alpha-Olefin Copolymer
[0038] Elastomeric EVA compositions in accordance may incorporate
one or more copolymers prepared from the polymerization of ethylene
and a C3 to C20 alpha-olefin.
[0039] Ethylene alpha-olefin copolymer in accordance with the
present disclosure may have a hardness determined in accordance
with ASTM D2240 in a range having a lower limit selected from any
of 10 Shore A, 15 Shore A, and 20 Shore A, to an upper limit
selected from any of 70 Shore A, 75 Shore A, and 80 Shore A, where
any lower limit may be paired with any upper limit.
[0040] Ethylene alpha-olefin copolymer in accordance with the
present disclosure may have a density determined according to ASTM
D792 in a range having a lower limit selected from any of 0.80
g/cm.sup.3, 0.85 g/cm.sup.3, and 0.88 g/cm.sup.3, to an upper limit
selected from any of 0.89 g/cm.sup.3, 0.90 g/cm.sup.3, and 0.95
g/cm.sup.3, where any lower limit may be paired with any upper
limit.
[0041] Ethylene alpha-olefin copolymer in accordance with the
present disclosure may have a melt flow index (MFI) at 190.degree.
C. and 2.16 kg as determined according to ASTM D1238 in a range
having a lower limit selected from any of 0.01 g/10 min, 0.05 g/10
min, and 0.1 g/10 min, 0.5 g/10 min, 1 g/10 min, 5 g/10 min and 10
g/10 min to an upper limit selected from any of 70 g/10 min, 75
g/10 min, and 100 g/10 min, where any lower limit may be paired
with any upper limit.
[0042] Elastomeric EVA compositions in accordance with the present
disclosure may contain an ethylene alpha-olefin copolymer at a
percent by weight (wt %) of the composition that ranges from a
lower limit of 5 wt % or 10 wt %, to an upper limit of 30 wt % or
60 wt %, where any lower limit may be paired with any upper
limit.
[0043] (C) Polyorganosiloxane
[0044] Elastomeric EVA compositions in accordance with the present
disclosure may incorporate a polyorganosiloxane. In one or more
embodiments, suitable polyorganosiloxanes include a linear chain,
branched, or three-dimensional structure, wherein the side groups
can include one or more of methyl, ethyl, propyl groups, vinyl,
phenyl, hydrogen, amino, epoxy, or halogen substituents. The
terminal groups of the polyorganosiloxane may include hydroxyl
groups, alkoxy groups, trimethylsilyl, dimethyldiphenylsilyl, and
the like. Polyorganosiloxanes in accordance with the present
disclosure may include one or more of dimethylpolysiloxane,
methylpolysiloxane, and the like.
[0045] Elastomeric EVA compositions in accordance with the present
disclosure may contain a polyorganosiloxane having a viscosity
measured at 25.degree. C. that ranges from a lower limit of 20 cP
or 40 cP, to an upper limit of 700,000 cP or 900,000 cP, where any
lower limit may be paired with any upper limit.
[0046] Elastomeric EVA compositions in accordance with the present
disclosure may contain a polyorganosiloxane at a percent by weight
(wt %) of the composition that ranges from a lower limit of 0.1 wt
% or 0.5 wt %, to an upper limit of 5 wt % or 10 wt %, where any
lower limit may be paired with any upper limit.
[0047] (D) Plasticizer
[0048] Elastomeric EVA compositions in accordance may incorporate a
plasticizer to improve the processability and adjust the hardness
of the elastomeric EVA. Plasticizers in accordance with the present
disclosure may include one or more of bis(2-ethylhexyl) phthalate
(DEHP), di-isononyl phthalate (DINP), bis (n-butyl) phthalate
(DNBP), butyl benzyl phthalate (BZP), di-isodecyl phthalate (DIDP),
di-n-octyl phthalate (DOP or DNOP), di-o-octyl phthalate (DIOP),
diethyl phthalate (DEP), di-isobutyl phthalate (DIBP), di-n-hexyl
phthalate, tri-methyl trimellitate (TMTM), tri-(2-ethylhexyl)
trimellitate (TEHTM-MG), tri-(n-octyl, n-decyl) trimellitate,
tri-(heptyl, nonyl) trimellitate, n-octyl trimellitate, bis
(2-ethylhexyl) adipate (DEHA), dimethyl adipate (DMD), mono-methyl
adipate (MMAD), dioctyl adipate (DOA)), dibutyl sebacate (DBS),
polyesters of adipic acid such as VIERNOL, dibutyl maleate (DBM),
di-isobutyl maleate (DIBM), benzoates, epoxidized soybean oils,
n-ethyl toluene sulfonamide, n-(2-hydroxypropyl) benzene
sulfonamide, n-(n-butyl) benzene sulfonamide, tricresyl phosphate
(TCP), tributyl phosphate (TBP), glycols/polyesters, triethylene
glycol dihexanoate, 3gh), tetraethylene glycol di-heptanoate,
polybutene, acetylated monoglycerides; alkyl citrates, triethyl
citrate (TEC), acetyl triethyl citrate, tributyl citrate, acetyl
tributyl citrate, trioctyl citrate, acetyl trioctyl citrate,
trihexyl citrate, acetyl trihexyl citrate, butyryl trihexyl
citrate, trihexyl o-butyryl citrate, trimethyl citrate, alkyl
sulfonic acid phenyl ester, 2-cyclohexane dicarboxylic acid
di-isononyl ester, nitroglycerin, butanetriol trinitrate,
dinitrotoluene, trimethylolethane trinitrate, diethylene glycol
dinitrate, triethylene glycol dinitrate, bis (2,2-dinitropropyl)
formal, bis (2,2-dinitropropyl) acetal, 2,2,2-trinitroethyl
2-nitroxyethyl ether, mineral oils, among other plasticizers and
polymeric plasticizers.
[0049] Elastomeric EVA compositions in accordance with the present
disclosure may contain a plasticizer at a percent by weight (wt %)
of the composition that ranges from a lower limit of 0.5 wt % or 2
wt %, to an upper limit of 10 wt % or 20 wt %, where any lower
limit may be paired with any upper limit.
[0050] (E) Rubber
[0051] Elastomeric EVA compositions in accordance may incorporate a
rubber component to increase the rubbery touch and increase the
coefficient of friction, depending on the end application. Rubbers
in accordance with the present disclosure may include one or more
of natural rubber, poly-isoprene (IR), styrene and butadiene rubber
(SBR), polybutadiene, nitrile rubber (NBR); polyolefin rubbers such
as ethylene-propylene rubbers (EPDM, EPM), and the like, acrylic
rubbers, halogen rubbers such as halogenated butyl rubbers
including brominated butyl rubber and chlorinated butyl rubber,
brominated isotubylene, polychloroprene, and the like; silicone
rubbers such as methylvinyl silicone rubber, dimethyl silicone
rubber, and the like, sulfur-containing rubbers such as
polysulfidic rubber; fluorinated rubbers; thermoplastic rubbers
such as elastomers based on styrene, butadiene, isoprene, ethylene
and propylene, styrene-isoprene-styrene (SIS),
styrene-ethylene-butylene-styrene (SEBS), styrene-butylene-styrene
(SBS), and the like, ester-based elastomers, elastomeric
polyurethane, elastomeric polyamide, and the like.
[0052] Rubbers in accordance with the present disclosure may have a
hardness determined in accordance with ASTM D2240 in a range having
a lower limit selected from any of 10 Shore A, 15 Shore A, and 20
Shore A, to an upper limit selected from any of 45 Shore A, 50
Shore A, and 55 Shore A, where any lower limit may be paired with
any upper limit.
[0053] Elastomeric EVA compositions in accordance with the present
disclosure may contain a rubber at a percent by weight (wt %) of
the composition that ranges from a lower limit of 0.5 wt % or 1 wt
%, to an upper limit of 20 wt % or 40 wt %, where any lower limit
may be paired with any upper limit.
[0054] In one or more embodiments, the elastomeric EVA composition
may have a melt flow index (MFI) at 190.degree. C. and 2.16 kg as
determined according to ASTM D1238 in a range having a lower limit
selected from any of 1 g/10 min, 2 g/10 min, 3 g/10 min, and 4 g/10
min, to an upper limit selected from any of 10 g/10 min, 15 g/10
min, 20 g/10 min, 25 g/10 min, and, where any lower limit may be
paired with any upper limit., where any lower limit may be paired
with any upper limit.
[0055] In one or more embodiments, the elastomeric EVA composition
may have a density determined according to ASTM D792 in a range
having a lower limit selected from any of 0.92 g/cm.sup.3, 0.93
g/cm.sup.3, and 0.94 g/cm.sup.3, to an upper limit selected from
any of 0.94 g/cm.sup.3, 0.95 g/cm.sup.3, and 0.96 g/cm.sup.3, where
any lower limit may be paired with any upper limit.
[0056] In one or more embodiments, the elastomeric EVA composition
exhibits a Shore A hardness as determined by ASTM D2240 that may
range from a lower limit of any of 40, 50, or 60 to an upper limit
of 70, 80, or 90 Shore A, where any lower limit may be paired with
any upper limit.
[0057] Filler
[0058] Polymeric compositions in accordance with the present
disclosure may be loaded with fillers that may include carbon
black, silica powder, calcium carbonate, talc, titanium dioxide,
clay, polyhedral oligomeric silsesquioxane (POSS), metal oxide
particles and nanoparticles, inorganic salt particles and
nanoparticles, recycled EVA, and mixtures thereof.
[0059] As defined herein, recycled EVA may be derived from regrind
materials that have undergone at least one processing method such
as molding or extrusion and the subsequent sprue, runners, flash,
rejected parts, and the like, are ground or chopped.
[0060] In one or more embodiments, polymeric compositions in
accordance with the present disclosure one or more fillers at a
parts per hundred of resin (phr) that ranges from a lower limit
selected from one of 5 phr, 10 phr, 15 phr, 20 phr, 25 phr, 30 phr,
35 phr, 40 pht, and 55 phr to an upper limit selected from one of
60 phr, 80 phr, 100 phr, 120 phr, 140 phr, 160 phr, 180 phr, 200
phr, and 220 phr where any lower limit can be used with any upper
limit.
[0061] Peroxide Agent
[0062] Polymer compositions in accordance with the present
disclosure may include one or more peroxide agents capable of
generating free radicals during polymer processing. For example,
peroxide agents may be combined with an EVA resin while reacting
the polymer such as during polymerization and/or curing. In one or
more embodiments, peroxide agents may include bifunctional
peroxides such as benzoyl peroxide; dicumyl peroxide; di-tert-butyl
peroxide; 00-Tert-amyl-0-2-ethylhexyl monoperoxycarbonate;
tert-butyl cumyl peroxide; tert-butyl 3,5,5-trimethylhexanoate
peroxide; tert-butyl peroxybenzoate; 2-ethylhexyl carbonate
tert-butyl peroxide; 2,5-dimethyl-2,5-di (tert-butylperoxide)
hexane; 1,1-di (tert-butylperoxide)-3,3,5-trimethylcyclohexane;
2,5-dimethyl-2,5 -di(tert-butylperoxide) hexyne-3;
3,3,5,7,7-pentamethyl-1,2,4-trioxepane; butyl 4,4-di
(tert-butylperoxide) valerate; di (2,4-dichlorobenzoyl) peroxide;
di(4-methylbenzoyl) peroxide; peroxide
di(tert-butylperoxyisopropyl) benzene; and the like.
[0063] Peroxide agents may also include benzoyl peroxide,
2,5-di(cumylperoxy)-2,5-dimethyl hexane,
2,5-di(cumylperoxy)-2,5-dimethyl
hexyne-3,4-methyl-4-(t-butylperoxy)-2-pentanol,
butyl-peroxy-2-ethyl-hexanoate, tert-butyl peroxypivalate, tertiary
butyl peroxyneodecanoate, t-butyl-peroxy-benzoate,
t-butyl-peroxy-2-ethyl-hexanoate,
4-methyl-4-(t-amylperoxy)-2-pentanol,4-methyl-4-(cumylperoxy)-2-pentanol,
4-methyl-4-(t-butylperoxy)-2-pentanone,
4-methyl-4-(t-amylperoxy)-2-pentanone,
4-methyl-4-(cumylperoxy)-2-pentanone,
2,5-dimethyl-2,5-di(t-butylperoxy)hexane,
2,5-dimethyl-2,5-di(t-amylperoxy)hexane,
2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,
2,5-dimethyl-2,5-di(t-amylperoxy)hexyne-3,
2,5-dimethyl-2-t-butylperoxy-5-hydroperoxyhexane,
2,5-dimethyl-2-cumylperoxy-5-hydroperoxy hexane,
2,5-dimethyl-2-t-amylperoxy-5-hydroperoxyhexane, m/p-alpha,
alpha-di[(t-butylperoxy)isopropyl]benzene, 1,3,5
-tris(t-butylperoxyisopropyl)benzene,
1,3,5-tris(t-amylperoxyisopropyl)benzene, 1,3,5-tris(cumy
lperoxyisopropyl)benzene,
di[1,3-dimethyl-3-(t-butylperoxy)butyl]carbonate,
di[1,3-dimethyl-3-(t-amylperoxy)butyl]carbonate,
di[1,3-dimethyl-3-(cumylperoxy)butyl]carbonate, di-t-amyl peroxide,
t-amyl cumyl peroxide, t-butyl-isopropenylcumyl peroxide,
2,4,6-tri(butylperoxy)-s-triazine,
1,3,5-tri[1-(t-butylperoxy)-1-methylethyl]benzene,
1,3,5-tri-[(t-butylperoxy)-isopropyl]benzene,
1,3-dimethyl-3-(t-butylperoxy)butanol,
1,3-dimethyl-3-(t-amylperoxy)butanol,
di(2-phenoxyethyl)peroxydicarbonate,
di(4-t-butylcyclohexyl)peroxydicarbonate, dimyristyl
peroxydicarbonate, dibenzyl peroxydicarbonate,
di(isobomyl)peroxydicarbonate, 3-cumylperoxy-1,3-dimethylbutyl
methacrylate, 3-t-butylperoxy-1,3-dimethylbutyl methacrylate,
3-t-amylperoxy-1,3-dimethylbutyl methacrylate,
tri(1,3-dimethyl-3-t-butylperoxy butyloxy)vinyl silane,
1,3-dimethyl-3-(t-butylperoxy)butyl
N-[1-{3-(1-methylethenyl)-phenyl) 1-methylethyl]carbamate,
1,3-dimethyl-3-(t-amylperoxy)butyl
N-[1-{3(1-methylethenyl)-phenyl}-1-methylethyl]carbamate,
1,3-dimethyl-3-(cumylperoxy))butyl
N-[1-{3-(1-methylethenyl)-phenyl}-1-methylethyl]carbamate, 1,
1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,
1-di(t-butylperoxy)cyclohexane, n-butyl
4,4-di(t-amylperoxy)valerate, ethyl 3,3-di(t-butylperoxy)butyrate,
2,2-di(t-amylperoxy)propane,
3,6,6,9,9-pentamethyl-3-ethoxycabonylmethyl-1,2,4,5-tetraoxacyclononane,
n-buty 1-4,4-bis(t-butylperoxy)valerate,
ethyl-3,3-di(t-amylperoxy)butyrate, benzoyl peroxide,
OO-t-butyl-O-hydrogen-monoperoxy-succinate,
OO-t-amyl-O-hydrogen-monoperoxy-succinate, 3,6,9,
triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (or methyl ethyl
ketone peroxide cyclic trimer), methyl ethyl ketone peroxide cyclic
dimer, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane,
2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl perbenzoate,
t-butylperoxy acetate,t-butylperoxy-2-ethyl hexanoate, t-amyl
perbenzoate, t-amyl peroxy acetate, t-butyl peroxy isobutyrate,
3-hydroxy-1,1-dimethyl t-butyl peroxy-2-ethyl hexanoate,
OO-t-amyl-O-hydrogen-monoperoxy succinate,
OO-t-butyl-O-hydrogen-monoperoxy succinate, di-t-butyl
diperoxyphthalate, t-butylperoxy (3,3,5-trimethylhexanoate),
1,4-bis(t-butylperoxycarbo)cyclohexane,
t-butylperoxy-3,5,5-trimethylhexanoate,
t-butyl-peroxy-(cis-3-carboxy)propionate, allyl
3-methyl-3-t-butylperoxy butyrate, OO-t-butyl-O-isopropylmonoperoxy
carbonate, OO-t-butyl-O-(2-ethyl hexyl)monoperoxy carbonate,
1,1,1-tris[2-(t-butylperoxy-carbonyloxy)ethoxymethyl]propane,
1,1,1-tris[2-(t-amylperoxy-carbonyloxy)ethoxymethyl]propane,
1,1,1-tris[2-(cumylperoxy-cabonyloxy)ethoxymethyl]propane,
OO-t-amyl-O-isopropylmonoperoxy carbonate,
di(4-methylbenzoyl)peroxide, di(3-methylbenzoyl)peroxide,
di(2-methylbenzoyl)peroxide, didecanoyl peroxide, dilauroyl
peroxide, 2,4-dibromo-benzoyl peroxide, succinic acid peroxide,
dibenzoyl peroxide, di(2,4-dichloro-benzoyl)peroxide, and
combinations thereof.
[0064] In one or more embodiments, polymeric compositions in
accordance with the present disclosure may contain one or more
peroxide agents at a parts per hundred of resin (phr) of that
ranges from a lower limit selected from one of 0.5 phr, 0.75 phr, 1
phr, 1.5 phr and 2 phr, to an upper limit selected from one of 2.5
phr, 2.75 phr, 3 phr, 3.5 phr and 4 phr, where any lower limit can
be used with any upper limit. Further, it is envisioned that the
concentration of the peroxide agent may be more or less depending
on the application of the final material.
[0065] Crosslinking Co-Agents
[0066] It is also envisioned that crosslinking co-agent may be
combined in the polymer composition during the curing processes.
Crosslinking co-agents creat additional reactive sites for
crosslinking. Therefore, the degree of polymer crosslinking may be
considerably increased from that normally obtained by greater
additions of peroxide. Generally co-agents increase the rate of
crosslinking. In one or more embodiments, the crosslinking
co-agents may include Triallyl isocyanurate (TAIL),
trimethylolpropane-tris-methacrylate (TRIM), triallyl cyanurate
(TAC) and combinations thereof.
[0067] In one or more embodiments, polymeric compositions in
accordance with the present disclosure may contain one or more
crosslinking co-agent at a parts per hundred resin (phr) that
ranges from a lower limit selected from one of 0.01 phr, 0.25 phr,
0.5 phr, 1 phr to an upper limit selected from one of 1.5 phr and 2
phr.
[0068] Blowing Agent
[0069] Polymeric compositions in accordance with the present
disclosure may include one or more blowing agents to produce
expanded polymeric compositions and foams. Blowing agents may
include solid, liquid, or gaseous blowing agents. In embodiments
utilizing solid blowing agents, blowing agents may be combined with
a polymer composition as a powder or granulate.
[0070] Blowing agents in accordance with the present disclosure
include chemical blowing agents that decompose at polymer
processing temperatures, releasing the blowing gases such as
N.sub.2, CO, CO.sub.2, and the like. Examples of chemical blowing
agents may include organic blowing agents, including hydrazines
such as toluenesulfonyl hydrazine, hydrazides such as
oxydibenzenesulfonyl hydrazide, diphenyl oxide-4,4'-disulfonic acid
hydrazide, and the like, nitrates, azo compounds such as
azodicarbonamide, cyanovaleric acid, azobis(isobutyronitrile), and
N-nitroso compounds and other nitrogen-based materials, and other
compounds known in the art.
[0071] Inorganic chemical blowing agents may include carbonates
such as sodium hydrogen carbonate (sodium bicarbonate), sodium
carbonate, potassium bicarbonate, potassium carbonate, ammonium
carbonate, and the like, which may be used alone or combined with
weak organic acids such as citric acid, lactic acid, or acetic
acid.
[0072] In one or more embodiments, polymeric compositions in
accordance with the present disclosure may contain one or more
blowing agents at a parts per hundred resin (phr) that ranges from
a lower limit selected from one of 1 phr, 1.5 phr, 2 phr, 2.5 phr
and 3 phr, to an upper limit selected from one of 3.5 phr, 4 phr,
4.5 phr, 5 phr, 5.5 phr and 6 phr, where any lower limit can be
used with any upper limit.
[0073] Blowing Accelerators
[0074] Polymeric compositions in accordance with the present
disclosure may include one or more blowing accelerators (also known
as kickers) that enhance or initiate the action of a blowing agent
by lower the associated activation temperature. For example,
blowing accelerators may be used if the selected blowing agent
reacts or decomposes at temperatures higher than 170.degree. C.,
such as 220.degree. C. or more, where the surrounding polymer would
be degraded if heated to the activation temperature. Blowing
accelerators may include any suitable blowing accelerator capable
of activating the selected blowing agent. In one or more
embodiments, suitable blowing accelerators may include cadmium
salts, cadmium-zinc salts, lead salts, lead-zinc salts, barium
salts, barium-zinc (Ba-Zn) salts, zinc oxide, titanium dioxide,
triethanolamine, diphenylamine, sulfonated aromatic acids and their
salts, and the like.
[0075] In one or more embodiments, polymeric compositions in
accordance with the present disclosure may contain one or more
blowing accelerators at a parts per hundred resin (phr) that ranges
from a lower limit selected from one of 0.1 phr, 0.25 phr, 0.5 phr,
1 phr, 2 phr, and 2.5 phr, to an upper limit selected from one of
1.5 phr, 2 phr, 2.5 phr, 3 phr, 3.5 phr, 4 phr, 4.5 phr and 5 phr,
where any lower limit can be used with any upper limit.
[0076] Additives
[0077] Polymer compositions in accordance with the present
disclosure may include additives that modify various physical and
chemical properties when added to the polymer composition during
blending that include one or more polymer additives such as
processing aids, lubricants, antistatic agents, clarifying agents,
nucleating agents, beta-nucleating agents, slipping agents,
antioxidants, compatibilizers, antacids, light stabilizers such as
HALS, IR absorbers, whitening agents, inorganic fillers, organic
and/or inorganic dyes, anti-blocking agents, processing aids,
flame-retardants, plasticizers, biocides, adhesion-promoting
agents, metal oxides, mineral fillers, glidants, oils,
anti-oxidants, antiozonants, accelerators, and vulcanizing
agents.
[0078] Preparation
[0079] Polymeric compositions in accordance with the present
disclosure may be prepared in any conventional mixture device. In
one or more embodiments, polymeric compositions may be prepared by
mixture in conventional kneaders, banbury mixers, mixing rollers,
twin screw extruders, and the like, in conventional EVA processing
conditions and subsequently cured or cured and expanded in
conventional expansion processes, such as injection molding or
compression molding.
[0080] In one or more embodiments, the EVA copolymer in accordance
with the present disclosure may be prepared in reactor. Ethylene
and vinyl acetate are added in a reactor to polymerize. In some
embodiments, the ethylene, vinyl acetate are polymerized by high
pressure radical polymerization, wherein peroxide agents act as
polymerization initiators. In some embodiments, the ethylene and
the vinyl acetate, and the peroxide agents are added at elevated
pressure into an autoclave or tubular reactor at a temperature of
between 80.degree. C. and 300.degree. C. and a pressure inside the
reactor between 500 bar and 3000 bar in some embodiments, and a
pressure between 1000 bar and 2600 bar in some embodiments. In
other embodiments, the copolymers may be produced by a solution
polymerization process.
[0081] As mentioned, one or more free-radical producing agents,
including any of those described above may be present during the
polymerization. Further, it is also understood that upon being
mixed with the other components forming the polymer composition,
the polymer composition may also be cured for example in the
presence of peroxides as well, including those discussed above, and
optionally, a crosslinking co-agent. For embodiments which include
expanded compositions, discussed below, the expanding and curing
may be in the presence of a blowing agent and a peroxide agent, and
optionally, a blowing accelerator or crosslinking co-agent. During
any of such curing steps, in one or more embodiments, the curing
may occur in full or partial presence of oxygen, such as described
in WO201694161A1, which is incorporated by reference in its
entirety.
[0082] Physical Properties
[0083] Polymer compositions in accordance with the present
disclosure may have good performance as a replacement for rubber
materials with acceptable performance at high and low temperatures,
with little or no odor, and comparable or lower density to standard
rubber formulations. In one or more embodiments, polymer
compositions may exhibit high flexibility, suitable hardness, good
abrasion resistance, high coefficient of friction, and soft touch.
In some embodiments, articles prepared from polymer compositions in
accordance with the present disclosure may take the form of
expanded or non-expanded polymer structures.
[0084] A cured non-expanded article that includes the polymer
compositions of the present disclosure may have a density as
determined by ASTM D-792 that may range of a lower limit of any of
0.7, 0.8, 0.9, or 1.0 to an upper limit of any of 1.0, 1.1, or 1.2
g/cm.sup.3, where any lower limit can be used with any upper
limit.
[0085] Cured non-expanded articles prepared by the polymer
compositions in accordance with the present disclosure may have a
hardness as determined by ASTM D2240 within a range having a lower
limit selected from one of 40, 50, or 60 Shore A, to an upper limit
selected from one of 60, 70, 80, and 90 Shore A, where any lower
limit may be paired with any upper limit.
[0086] Cured non-expanded articles prepared by the polymer
compositions in accordance with the present disclosure may have an
abrasion resistance as determined by ISO 4649:2017 measured with a
load of 10N within a range having a lower limit selected from one
of 10, 20, 40, 80, to an upper limit selected from one of 100
mm.sup.3, 150 mm.sup.3, 200 mm.sup.3, or 250 mm.sup.3, where any
lower limit may be paired with any upper limit.
[0087] Cured non-expanded articles prepared by the polymer
compositions in accordance with the present disclosure may have an
elongation at break as determined by ASTM D638 that is at least
200%, 250%, or 300%.
[0088] Further, as mentioned, it is also envisioned that the
elastomeric EVA compositions may be expanded and cured, such as
with the described blowing agent and peroxide agent. Expanded
articles prepared by the polymer compositions in accordance with
the present disclosure may have a density as determined by ASTM
D-792 within a range having a lower limit selected from one of 0.05
g/cm.sup.3, 0.12 g/cm.sup.3, 0.2 g/cm.sup.3, 0.25 g/cm.sup.3, 0.5
g/cm.sup.3, to an upper limit selected from one of 0.4 g/cm.sup.3,
0.5 g/cm.sup.3, 0.6 g/cm.sup.3, 0.65 g/cm.sup.3, 0.70 g/cm.sup.3,
0.90 g/cm.sup.3 where any lower limit may be paired with any upper
limit.
[0089] Expanded articles prepared by the polymer compositions in
accordance with the present disclosure may have an Asker C hardness
as determined by ABNT NBR 14455:2015 in the range having a lower
limit of any of 20, 30, 40 or 50 Asker C and an upper limit of any
60, 70, 80, or 90 Asker C, where any lower limit can be paired with
any upper limit.
[0090] Expanded articles prepared by the polymer compositions in
accordance with the present disclosure may have a permanent
compression set (PCS) as determined by D395:2016 Method B within a
range having a lower limit selected from one of 20%, 30%, 40%, or
50% to an upper limit selected from one of 60%, 70%, 80%, 90%, or
100% where any lower limit may be paired with any upper limit.
[0091] Expanded articles prepared by the polymer compositions in
accordance with the present disclosure may have a rebound as
determined by ABNT NBR 8619:2015 within a range having a lower
limit selected from one of 30%, 35%, 40%, 45%, and 50% to an upper
limit selected from one of 50%, 60%, 70%, and 80%, where any lower
limit may be paired with any upper limit.
[0092] Expanded articles prepared by the polymer compositions in
accordance with the present disclosure may have a shrinkage at
70.degree. C.*1 h using the PFI method (PFI "Testing and Research
Institute for the Shoe Manufacturing Industry" in
Pirmesens--Germany) within a range having a lower limit selected
from one of 0.1%, 1%, 1.5%, and 5% to an upper limit selected from
one of 4%, 5%, 6%, and 7%, where any lower limit may be paired with
any upper limit.
[0093] The PFI method may be used in the industry for shrinkage
measurements and is detailed below:
[0094] Equipment: [0095] oven with forced air circulation [0096]
pachymeter [0097] ruler for marking of specimens or template [0098]
thickness gauge
[0099] Sample
[0100] Three specimens of dimensions of at least 100.times.100 mm
should be evaluated of each sample.
[0101] Procedure
[0102] The specimens may be conditioned at a temperature of
23.+-.2.degree. C. and a relative humidity of 50.+-.5% for 1 hour.
The approximate thickness of the specimens is measured.
[0103] Using a ruler or template, the points A, B, C and D are
marked on each of the specimens as shown in FIG. 2.
[0104] The initial length (C.sub.i) is measured with a pachymeter,
to the nearest 0.01 mm, in direction A (segments A-B and C-D) and
in the direction B (segments A-C and B-D).
[0105] The specimens are then held at 70.degree. C. for 1 hour in a
forced air circulation oven.
[0106] After the exposure period, the specimens are removed from
the oven and conditioned at a temperature of 23.+-.2.degree. C. and
a relative humidity of 50.+-.5% for 60 minutes.
[0107] The final length (C.sub.f) is measured with a caliper, to
the nearest 0.01 mm, in direction A (segments A-B and C-D) and
direction B (segments A-C and B-D).
[0108] The average initial length (C.sub.im) is calculated in the A
direction as the average of the A-B and C-D segments and in the B
direction as the average of the A-C and B-D segments for each of
the specimens.
[0109] The average final length (C.sub.fm) is calculated in the A
direction as the average of the A-B and C-D segments and the B
direction as the average of the A-C and B-D segments for each of
the specimens.
[0110] Results
[0111] The shrinkage of the expanded EVA is given by the following
equation, expressed as a percentage to the nearest 0.1%.
Shrinkage %=(C.sub.im-C.sub.fm).times.100/C.sub.im
[0112] Where:
[0113] C.sub.im=initial length average (mm)
[0114] C.sub.fm=final length average (mm)
[0115] The final EVA shrinkage result will be calculated for the
directions A and B as the average of the shrinkage values
calculated for each specimen.
[0116] Note: The PFI recommends acceptable maximum values for
shrinkage of expanded materials in directions A and B (FIGS. 1):
[0117] 3% for materials with a density up to 0.6 g/cm.sup.3 [0118]
2% for materials with a density above 0.6 g/cm.sup.3
[0119] Expanded articles prepared by the polymer compositions in
accordance with the present disclosure may have an abrasion
resistance as determined by ISO 4649 measured with a load of 5N
within a range having a lower limit selected from one of 40
mm.sup.3, 80 mm.sup.3, 120 mm.sup.3, 150 mm.sup.3, 200 mm.sup.3, or
400 mm.sup.3, to an upper limit selected from one of 300 mm.sup.3,
600 mm.sup.3, or 700 mm.sup.3, where any lower limit may be paired
with any upper limit.
[0120] Expanded articles prepared by the polymer composition in
accordance with the present disclosure may have an elongation at
break as determined by ASTM D638 that is at least 300%, 350%, or
400%.
[0121] Applications
[0122] In one or more embodiments, polymer compositions can be used
in various molding processes, including extrusion molding,
injection molding, compression molding, thermoforming, cast film
extrusion, blown film extrusion, foaming, extrusion blow-molding,
injection blow-molding, ISBM (Injection Stretched Blow-Molding),
pultrusion, 3D printing, rotomolding, double expansion process, and
the like, to produce manufactured articles.
[0123] Polymer compositions in accordance with the present
disclosure may also be formulated for a number of polymer articles,
including the production of insoles, midsole, soles, hot-melt
adhesives, primers, in civil construction as linings, industrial
floors, acoustic insulation. Polymeric compositions in accordance
with the present disclosure may be formed into articles used for a
diverse array of end-uses including shoe soles, midsoles, outsoles,
unisoles, insoles, monobloc sandals and flip flops, and full EVA
footwear.
[0124] Other applications may include seals, hoses, gaskets, foams,
foam mattresses, furniture, electro-electronic, automotive,
packaging, EVA tires, bras, mats, paperboards, sportive articles,
toys, swimming accessories, legs floats, yoga blocks, dumbbell
gloves, gym steps, rodo sheets, kimono strips, sandpapers, finger
protectors, wall protectors, finger separators, educational games
and articles, decorative panels, EVA balls, twisted Hex stools,
slippers, pillow, sponges, seats, cycling bib pad, protective
covers, carpets, aprons and others.
EXAMPLES
[0125] In the following examples, polymer compositions formulations
where prepared and assayed to study various physical
properties.
Example 1
Production of Biobased Copolymers of Ethylene Vinyl Acetate
[0126] A biobased copolymer of ethylene and vinyl acetate according
to the present invention was prepared using ethylene obtained from
the dehydration of ethanol obtained from sugarcane. Dehydration of
ethanol to produce ethylene was conducted in a series of four fixed
bed adiabatic reactors connected in series with temperature varying
from 350.degree. C. to 480.degree. C. and a pressure of 3 to 10
atm, using an alumina catalyst. The reaction product is
subsequently purified by cryogenic distillation and a polymer grade
ethylene is obtained.
[0127] This copolymer of ethylene and vinyl acetate was produced in
a high pressure tubular reactor with 1.110 m in length and 50 mm in
diameter. The ethylene is injected at a flow rate of 8.5
tonnes/hour into the reactor and vinyl acetate in injected at a
flow rate of 2000 kg/hour. The mixture is compressed in a
hypercompressor to 2400 bar and preheated at 130.degree. C. A
mixture of tertiary-butyl peroxypivalate/t-Butyl
Peroxy-2-ethyl-hexanoate/00-Tert-amyl-0-2-ethylhexyl
monoperoxycarbonate was used as initiator. The reaction temperature
was varied between 190.degree. C. and 250.degree. C., with a
production of 8.5 tonnes/hour of EVA copolymer. Table 1 presents
the properties of the resulting biobased EVA.
TABLE-US-00001 TABLE 1 Biobased EVA obtained according to the
present disclosure Properties Unit Value Vinyl acetate wt % 18.7
content Melt Index g/10 min 1.95 (190.degree. C.@2.16 kg) Density
g/cm.sup.3 0.941 Hardness Shore A 89 VICAT .degree. C. 64 softening
temperature Biobased carbon % 88 content
Example 2
Preparation of Elastomeric EVA
[0128] In the following example, an elastomeric EVA formed with
bio-based EVA in accordance with the present disclosure, and
commercially available as SVT2145R from Braskem SA, was tested to
determine the properties set forth in Table 2.
TABLE-US-00002 TABLE 2 Properties of elastomeric EVA in accordance
with the present disclosure Properties Unit Value Vinyl acetate wt
% 15 content Melt Index g/10 min 1.9 (190.degree. C.@2.16 kg)
Density g/cm.sup.3 0.915 Hardness Shore A 79 VICAT .degree. C. 43
softening temperature Biobased carbon % 48 content
Example 3
Preparation of Cured Non-Expanded Articles
[0129] In the following example, curable polymeric composition
formulations were prepared in a kneader model XSN-5 QUANZHOU
YUCHENGSHENG MACHINE CO., LTD at a temperature of 100.degree. C.
and subsequently laminated in a cylinder (open-mix) and pressed and
cured in a hydraulic press model LPB-100-AQ-EVA from Luxor Ind
stria de Maquinas Ltda at 175.degree. C. for 7 min to produce
plaques of 10.times.10 cm, which were assayed to study various
physical properties. Curable polymeric composition formulations,
including also a mixture of biobased elastomeric EVA and biobased
EVA, are shown in Table 3.
TABLE-US-00003 TABLE 3 Curable non-expanded polymer compositions C1
C2 Material PHR PHR Elastomeric EVA of example 2 100 50 Biobased
EVA produced in 0 50 example 1 Stearic Acid 1 1 Peroxide agent
(bis-peroxide 2 2 40%) Total 103 103
Samples were assayed for hardness (Shore A and Shore D), density,
abrasion resistance and biobased content, and the results are shown
in Table 4.
TABLE-US-00004 TABLE 4 Properties of cured non-expanded polymer
compositions Properties Unit C1 C2 Hardness Shore D Shore D 24 31
Hardness Shore A Shore A 82 84 Density g/cm.sup.3 0.898 0.931
Abrasion mm.sup.3 41 28 Biobased carbon content % 47 68
Example 4
Preparation of Expanded Articles
[0130] In the following example, expandable polymeric composition
formulations were prepared in a kneader model XSN-5 QUANZHOU
YUCHENGSHENG MACHINE CO., LTD at a temperature of 105.degree. C.
and subsequently laminated in a cylinder (open-mix) and pressed and
cured in a hydraulic press model LPB-100-AQ-EVA from Luxor Ind
stria de Maquinas Ltda at 175.degree. C. for 7 min and expanded at
different expansion rates to produce plaques, which were assayed to
study various physical properties. Exapandable polymeric
composition formulations are shown in Table 5.
TABLE-US-00005 TABLE 5 Expandable polymer compositions C3 C4 C5 C6
Material PHR PHR PHR PHR Biobased elastomeric EVA of 100 100 100 50
example 2 Biobased EVA produced in 0 0 0 50 example 1 Calcium
Carbonate 10 10 10 10 Zinc Oxide 2 2 2 2 Stearic Acid 1 1 1 1
Blowing Agent 1.3 2.2 1.6 3 (azodicarbonamide) Peroxide agent
(bis-peroxide 2 2 2 2 40%) Total 116.3 117.2 116.6 118
[0131] Samples were assayed for hardness (Shore A and Asker C),
density, abrasion resistance, compression set, shrinkage, rebound
and biobased carbon content, and the results are shown in Table
6.
TABLE-US-00006 TABLE 6 Properties of expanded polymer compositions
Properties Unit C3 C4 C5 C6 Expansion Rate % 40 60 80 45 Hardness
Asker C Asker C 54 42 26 59 Hardness Shore A Shore A 35 26 16 43
Density g/cm.sup.3 0.281 0.2 0.123 0.268 Abrasion mm.sup.3 87 134
215 85 Compression Set % 54 60 67 52 Shrinkage % 0.5 1 1 1 Rebound
% 42 45 49 41 Biobased carbon content % 46 46 46 66
[0132] Although only a few example embodiments have been described
in detail above, those skilled in the art will readily appreciate
that many modifications are possible in the example embodiments
without materially departing from this invention. Accordingly, all
such modifications are intended to be included within the scope of
this disclosure as defined in the following claims. In the claims,
means-plus-function clauses are intended to cover the structures
described herein as performing the recited function and not only
structural equivalents, but also equivalent structures. Thus,
although a nail and a screw may not be structural equivalents in
that a nail employs a cylindrical surface to secure wooden parts
together, whereas a screw employs a helical surface, in the
environment of fastening wooden parts, a nail and a screw may be
equivalent structures. It is the express intention of the applicant
not to invoke 35 U.S.C. .sctn. 112, paragraph 6 for any limitations
of any of the claims herein, except for those in which the claim
expressly uses the words `means for` together with an associated
function.
* * * * *