U.S. patent application number 16/438887 was filed with the patent office on 2019-09-26 for renewable and cost-effective fillers for polymeric materials.
The applicant listed for this patent is King Abdulaziz City for Science and Technology. Invention is credited to Fares D. ALSEWAILEM, Yazeed A. BINKHEDER.
Application Number | 20190292354 16/438887 |
Document ID | / |
Family ID | 48086401 |
Filed Date | 2019-09-26 |
United States Patent
Application |
20190292354 |
Kind Code |
A1 |
ALSEWAILEM; Fares D. ; et
al. |
September 26, 2019 |
RENEWABLE AND COST-EFFECTIVE FILLERS FOR POLYMERIC MATERIALS
Abstract
Polymer composites are provided, and more particularly, polymer
composites of ground date pits disposed in a polymer matrix. The
composites can be formed by a process of preparing reinforced
polymer composites having a fibril melt fracture surface, including
blending a mixture of date pit particulate with a thermoplastic
polymer; melting the mixture; and forcing the melt through a die to
produce the polymer composite having a fibril containing
surface.
Inventors: |
ALSEWAILEM; Fares D.;
(Riyadh, SA) ; BINKHEDER; Yazeed A.; (Riyadh,
SA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
King Abdulaziz City for Science and Technology |
Riyadh |
|
SA |
|
|
Family ID: |
48086401 |
Appl. No.: |
16/438887 |
Filed: |
June 12, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15870401 |
Jan 12, 2018 |
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16438887 |
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13275977 |
Oct 18, 2011 |
9902842 |
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15870401 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L 99/00 20130101;
C08L 25/06 20130101; C08L 99/00 20130101; C08L 99/00 20130101; C08L
99/00 20130101; C08L 2205/14 20130101; C08L 77/00 20130101; C08L
99/00 20130101; C08L 23/06 20130101; C08L 99/00 20130101; C08J
5/045 20130101; C08L 69/00 20130101; C08L 27/06 20130101; C08K
5/0008 20130101; C08J 2323/06 20130101; C08L 99/00 20130101; C08L
25/06 20130101; C08L 99/00 20130101; C08J 2325/06 20130101; C08L
27/06 20130101; C08K 11/00 20130101; C08L 69/00 20130101; C08L
23/06 20130101; C08L 25/06 20130101; C08L 97/02 20130101; C08L
77/00 20130101; C08L 23/12 20130101; C08L 67/025 20130101; C08L
27/06 20130101; C08L 23/06 20130101; C08L 99/00 20130101; C08L
99/00 20130101; C08L 97/02 20130101; C08L 51/06 20130101; C08L
55/02 20130101; C08L 33/12 20130101 |
International
Class: |
C08K 11/00 20060101
C08K011/00; C08J 5/04 20060101 C08J005/04; C08K 5/00 20060101
C08K005/00; C08L 99/00 20060101 C08L099/00; C08L 27/06 20060101
C08L027/06; C08L 25/06 20060101 C08L025/06; C08L 23/06 20060101
C08L023/06; C08L 69/00 20060101 C08L069/00; C08L 77/00 20060101
C08L077/00 |
Claims
1. A process of preparing a reinforced polymer composite,
comprising: solution blending a mixture of date pit particulate, a
solution of a thermosetting polymer, and a coupling agent of
di-phenylmethane; and removing solvent from the solution.
2. The process of claim 1, wherein the reinforced polymer composite
has a tensile strength varying no more than about 10% from that of
the thermosetting polymer.
3. The process of claim 1, wherein the date pit particulate has an
average size of between about 0.25 mm and 1.0 mm.
4. The process of claim 1, wherein the date pit particulate
comprises particulate from fruit of Phoenix dactylifera L., variety
khlaas or sekari.
5. The process of claim 1, wherein the date pit particulate is
present in an amount of between about 1 and about 40 wt % based on
a weight of the composition.
6. The process of claim 1, wherein the thermosetting polymer is
selected from the group consisting of epoxies, vinyl esters, and
polyesters.
7. The process of claim 1, wherein the date pit particulate
comprises particulate from fruit of Phoenix dactylifera L., variety
sekari, present in an amount from 5 wt % to 30 wt % based on a
weight of the composition.
8. The process of claim 1, wherein the date pit particulate
comprises particulate from fruit of Phoenix dactylifera L., variety
khlaas, present in an amount from 10 wt % to 40 wt % based on a
weight of the composition.
9. The process of claim 1, further comprising blending a toughness
modifier including ethylene/propylene grafted with maleic anhydride
with the mixture.
10. The process of claim 1, further comprising blending a toughness
modifier including maleated polyolefins elastomers with the
mixture.
Description
FIELD OF THE INVENTION
[0001] The invention relates to a polymer composite, and more
particularly, to a polymer composite of ground date pits disposed
in a polymer matrix.
BACKGROUND OF THE INVENTION
[0002] Fillers are routinely used by polymer and plastic industry
to reduce the cost of end products and to enhance some desired
properties, such as physical and mechanical properties. However,
conventional filler materials can be costly and therefore need to
be processed in an efficient manner, and conventional inorganic
fillers, such as aluminium trihydroxide and the like may pose
environment risks when used as polymer fillers.
[0003] Formulation of biocomposites has been an attractive endeavor
for researchers in the last decade. There are several advantages,
either environmental or economical, of using biocomposites over
ordinary composites, especially those based on thermoplastics
matrices, for various applications such as structural and food
packaging. The biodegradability feature of such composites offers a
solution for the problem of municipal waste management. Besides the
biodegradability of polymers filled with biomaterials, the
availability of these fillers, normally of agricultural residue
origin, at very low cost levels makes the production of these
composites economically feasible.
[0004] Several biocomposite systems of thermoplastic matrices and
bio-fillers have been reported in the literature, wherein various
bio-fillers, such as wheat straw, corncob, rice husk, and sugarcane
bagasse were incorporated with polymer matrices, such as
polypropylene, high-density polyethylene (HDPE), low-density
polyethylene, and polyvinyl chloride. From an economic point of
view, incorporating a cost-effective filler in a polymer will only
be feasible if it does not drastically alter the main matrix-resin
characteristics, such as mechanical properties.
[0005] Saudi Arabia is well recognized for its palm trees (Phoenix
dactylifera L.). In addition, Saudi Arabia is among the largest
world producers of date fruit, 4700,000 MT per year. On the
consumption of date fruit as a main daily meal in almost each Saudi
dwelling, date pits are usually discarded as materials with no use
or value. Nevertheless, these presumably designated waste
materials, i.e., date pits, contain important constituents such as
oils (up to 10%), minerals (considerably rich in potassium), and
fibers (46.4%) that may be utilized for specific purposes.
[0006] Ghazanfari et al. ("Thermal and Mechanical Properties of
Blends and Composites from HDPE and Date Pits Particles", Journal
of Composite Materials, 42(1) (2008); pp. 77-89) disclose
formulating polymer-date pits composites based on HDPE as the
hosting polymer, and conclude that incorporating date pit flour
with HDPE tends to decrease the melt flow index (MFI), and at the
same time increase the thermal conductivity of the resulting
composites. The date pits investigated by Ghazanfari et al. are of
the Abdoulahi cultivar, which demonstrate reductions in tensile
strength as compared to non-composited (neat) polymer, on
increasing weight percentages of date pit flour in the
composites.
[0007] U.S. Pat. No. 4,011,130 to Worden discloses waterlaid sheets
comprising essential solids consisting of (I) elastomeric
(polyurethane) binder, and (II) nonelastomeric solids comprising
inflexible, non-fibrous, rounded, particulate fillers (which may be
vegetable flours prepared from peach pits, apricot pits and cherry
pits) and a fibrous reinforcing component. The waterlaid sheets are
useful as substitutes for leather in the manufacture of footwear,
particularly as the outsole or insole portion of a shoe. However,
no comparison of tensile strength between the neat polymer and the
polymer composite is provided.
[0008] Accordingly, polymer and plastic industries would benefit
from a demonstration of affordable, efficient bio-fillers which
would reduce the cost of the final products and yet not diminish
the strength characteristics of the polymer, as compared to the
corresponding non-composited polymer.
SUMMARY OF THE INVENTION
[0009] In a first aspect of the invention, a process of preparing a
reinforced polymer composite having a fibril melt fracture surface,
comprises blending a mixture of date pit particulate with a
thermoplastic polymer; melting the mixture; and forcing the melt
through a die to produce the polymer composite having a fibril
containing surface.
[0010] In another aspect the invention, composition comprises a
mixture of date pit particulate from the fruit of Phoenix
dactylifera L., variety khlaas or sekari, and a thermosetting
polymer selected from the group consisting of epoxies, vinyl esters
and polyesters.
[0011] In yet another aspect of the invention, a process of
preparing a reinforced polymer composite, comprises solution
blending a mixture of date pit particulate from the fruit of
Phoenix dactylifera L., variety khlaas or sekari, and a solution of
a thermosetting polymer, and removing solvent from the
solution.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The present invention is described in the detailed
description which follows, in reference to the noted plurality of
drawings by way of non-limiting examples of exemplary embodiments
of the present invention.
[0013] FIGS. 1(a)-(c) show scanning electron micrographs of melt
fracture surfaces of various loadings of date pit particulate in
high density polyethylene matrices;
[0014] FIGS. 2(a) and (b) show scanning electron micrographs of
melt fracture surfaces of various loadings of date pit particulate
in polystyrene matrices;
[0015] FIGS. 3(a) and (b) show scanning electron micrographs of
melt fracture surfaces of composites of polystyrene, date pit
particulates and two different compounding modifiers; and
[0016] FIG. 4 shows a graph comparing the Tensile Strengths of
various date pit particulate/high density polyethylene composites
at various particulate loading levels.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The invention relates to composites of polymers filled with
naturally occurring fillers. More specifically, it has been found
that the fruit of dates, i.e. the date pits, can be ground into
particulate and blended with polymers to form composites having
unique surface characteristics upon melt processing of the
composites, without sacrificing the overall strength
characteristics of the polymers, as compared to the corresponding
non-composited polymers.
[0018] Advantageously, the processes and products of the present
invention provide inexpensive, renewable sources for polymer
fillers which can act to reduce the overall cost of polymeric
articles made from the composites, but also provide an avenue for
reducing waste from the consumption of dates, commonly an every-day
occurrence in many Middle Eastern households.
[0019] In implementing the present invention a mixture of date pit
particulate can be blended with a thermoplastic polymer, the
mixture melted, in for example a melt extruder as is known in the
art, and the melt is forced through an extrusion die to produce a
polymer composite having a fibril containing surface. Upon
examination of the surface using scanning electron microscopy
(SEM), it is found that the surface of the melt processed
composites demonstrate a unique, fibril-containing melt fracture
surface, which can enhance physical characteristics of the extruded
polymer compositions, such as toughness and stiffness, as compared
to neat polymers.
[0020] In embodiments, the date pit particulate can be particulate
from the fruit of Phoenix dactylifera L., variety khlaas or sekari,
which varieties are commonly consumed in large quantities in Middle
Eastern households, such as in Saudi Arabia. The date pits are
advantageously ground or chopped to particulate of an average size
of between about 0.25 mm and 1.0 mm.
[0021] The melt processing according to the present invention can
be practiced with a number of different thermoplastic polymers to
form the composite matrix, such as those selected from the group
consisting of polystyrene, polyethylene, polypropylene,
polyethylene terephthalate, polyvinyl chloride,
polymethylmethacrylate, polycarbonate,
acrylonitrile-butadiene-styrene (ABS) and polyamide. Those skilled
in the art will recognize that many other such thermoplastic
polymers can be melt processed into date pit particulate/polymer
composites and articles, such as molded articles, according to the
present invention.
[0022] The concentration or loading of the date pit particulate in
the composite is not particularly limited, and can advantageously
be in an amount of between about 1 and about 40 wt % based on the
weight of the composite. For example when the polymer is high
density polyethylene, the composite can contain from 5 wt % to 30
wt % of date pit particulate from the variety sekari; or from 10 wt
% to 40 wt % of date pit particulate from the variety khlaas. When
the polymer is polystyrene, the composite can contain from 10 wt %
to 40 wt % of date pit particulate from the variety khlaas, or from
5 wt % to 30 wt % of date pit particulate from the variety
sekari.
[0023] In any event, the polymer composite demonstrates Tensile
Strength varying no more than about 10% from that of the
uncomposited polymer. Unexpectedly, date pit particulate/polymer
composites can be successfully produced from thermosetting polymers
too, such as from the group consisting of epoxies, vinyl esters and
polyesters.
[0024] In this embodiment, a reinforced polymer composite is formed
by solution blending a mixture of date pit particulate from the
fruit of Phoenix dactylifera L., variety khlaas or sekari, and a
solution of a thermosetting polymer, and removing solvent from the
solution. Particulate loadings can advantageously be from about 5
wt % to about 40 wt %, depending on the date pit
particulate/polymer combination.
EXAMPLES
Example 1--High Density Polyethylene (HDPE)/Sekari (S)
Composites
[0025] Composites were formulated by melt extrusion where 10 to 40
wt % of date pit particulate was dispersed in a polymer matrix
(HDPE). FIG. 1 shows the morphology of the fractured surface of the
blends. It is clearly seen that some fibril morphology has
developed. As far the mechanical properties, compounding polymer
with date pits particulate did not affect important properties such
as tensile strength (ASTM D-638), even at relatively high filler
content, e.g 40 wt % (FIG. 4).
Example 2--Polystyrene (PS)/Date Pit Composites
[0026] Samples of PS/date pit particulate composites were prepared
and the morphology of the blends' melt fracture surfaces was
studied by scanning electron microscope (SEM). FIG. 2 shows the
morphology of PS/date pit particulates at 30 wt % particulate
loading. The morphology exhibited some fibril-like characteristics,
and satisfactory adhesion between date pit particulates and polymer
matrix.
Example 3--Coupling agent composites
[0027] Coupling agents and compatibilizers such as isocynate,
silane, and di-phenylmethane were compounded with the polymer/date
pit particulate composites to enhance the surface morphology. FIG.
3(a) shows effect of adding di-phenylmethane (DPHM) to the melt
fracture surface morphology of the composite containing 30 wt % K
and 70 wt % PS.
Example 4--Toughness Modifier Composites
[0028] Toughness modifiers were added to the composites to
compensate for the reduction in some properties, such as impact
strength using some melated polyolefins elastomers (e.g.
ethyelene/propylene grafted with maleic anhydride, indicated as
EP-g-MA). FIG. 3(b) shows the morphology of melt fracture surface
of a composite containing 30 wt % K and 70 wt % PS.
[0029] The foregoing examples have been provided for the purpose of
explanation and should not be construed as limiting the present
invention. While the present invention has been described with
reference to an exemplary embodiment, Changes may be made, within
the purview of the appended claims, without departing from the
scope and spirit of the present invention in its aspects. Also,
although the present invention has been described herein with
reference to particular materials and embodiments, the present
invention is not intended to be limited to the particulars
disclosed herein; rather, the present invention extends to all
functionally equivalent structures, methods and uses, such as are
within the scope of the appended claims.
* * * * *