IES84698Y1 - A process for preparing a wood-polyolefin composite - Google Patents
A process for preparing a wood-polyolefin compositeInfo
- Publication number
- IES84698Y1 IES84698Y1 IE2006/0932A IE20060932A IES84698Y1 IE S84698 Y1 IES84698 Y1 IE S84698Y1 IE 2006/0932 A IE2006/0932 A IE 2006/0932A IE 20060932 A IE20060932 A IE 20060932A IE S84698 Y1 IES84698 Y1 IE S84698Y1
- Authority
- IE
- Ireland
- Prior art keywords
- polyolefin
- wood
- creep
- composite
- amount
- Prior art date
Links
- 229920000098 polyolefin Polymers 0.000 title claims description 184
- 239000002131 composite material Substances 0.000 title claims description 103
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000003638 reducing agent Substances 0.000 claims description 48
- 239000000945 filler Substances 0.000 claims description 27
- 229920002678 cellulose Polymers 0.000 claims description 26
- 239000001913 cellulose Substances 0.000 claims description 26
- 239000002023 wood Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000000875 corresponding Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 17
- -1 fatty acid esters Chemical class 0.000 description 14
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 description 13
- 239000004698 Polyethylene (PE) Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 11
- 229910000077 silane Inorganic materials 0.000 description 11
- 239000004707 linear low-density polyethylene Substances 0.000 description 10
- 239000004594 Masterbatch (MB) Substances 0.000 description 9
- 229920000092 linear low density polyethylene Polymers 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920001112 grafted polyolefin Polymers 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 229910052570 clay Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 239000011121 hardwood Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- HPSUPGAVFFFPMQ-UHFFFAOYSA-N 1,2,3,4,6,7,10-heptachlorododecane Chemical compound CCC(Cl)CCC(Cl)C(Cl)CC(Cl)C(Cl)C(Cl)CCl HPSUPGAVFFFPMQ-UHFFFAOYSA-N 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 description 2
- 240000005781 Arachis hypogaea Species 0.000 description 2
- 235000018262 Arachis monticola Nutrition 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene (UHMWPE) Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000011093 chipboard Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000003247 decreasing Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000011068 load Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 235000020232 peanut Nutrition 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-Hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N N-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 206010041662 Splinter Diseases 0.000 description 1
- HWKQNAWCHQMZHK-UHFFFAOYSA-N Trolnitrate Chemical compound [O-][N+](=O)OCCN(CCO[N+]([O-])=O)CCO[N+]([O-])=O HWKQNAWCHQMZHK-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 230000000111 anti-oxidant Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 230000003115 biocidal Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001143 conditioned Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- KARVSHNNUWMXFO-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane;hydrate Chemical compound O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O KARVSHNNUWMXFO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-M stearate Chemical class CCCCCCCCCCCCCCCCCC([O-])=O QIQXTHQIDYTFRH-UHFFFAOYSA-M 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
Description
A process for preparing a wood-polyolefin composite
Introduction
The present invention relates to a process for preparing a wood-polyolefin composite
having reduced creep; the composite comprising a cellulose-based filler in the amount
of between 20% and 80% by weight, a polyolefin in the amount of between 80% and
% by weight wherein at least 25% of the polyolefin is recycled polyolefin and an
amount of creep reducing agent. The invention also relates to a process for preparing
a wood-polyolefin composite article and to a wood-polyolefin composite and wood-
polyolefin composite article prepared by these processes.
Composite materials consisting of a mixture of cellulose-based filler and a polymeric
material such as a polyolefin are well known. In the specification the term “cellulose-
based filler" refers to all types of material containing cellulose and includes but is not
limited to wood flour, fibre and particles and other natural materials. A polyolefin is a
polymer of the alkene family of hydrocarbons. In the specification the term “by weight”
refers to by weight of the wood-polyolefin composite unless where otherwise specified.
Wood-polyolefin composites generally comprise at least a portion of recycled
polyolefin and are therefore a cost effective way of utilising recycled polymers. Wood-
polyolefin composites are beneficial in that they can be easily substituted for a number
of applications requiring wood. Furthermore, in some aspects they are more
advantageous than wood in that they have both a longer life and require lower
maintenance than wood and do not splinter or crack.
One of the main problems with wood-polyolefin composites however is that they
experience problems caused by creep of the polyolefin component. “Creep“ is
defined as the time dependent deformation of a material in response to an applied
stress and thus can be caused by a number of different factors. Creep in the wood-
polyolefin composites usually occurs when unsuitable polyolefins such as lower
molecular weight and lower density polyolefins or recycled polyolefins are used.
Recycled polyolefins in general have reduced molecular weight which is caused by
UV light and oxygen present breaking the carbon bonds within the polymeric chains
during the initial use of the polyolefin and by heat processing during recycling. One of
the main problems with using recycled polyolefins is that due to their lower molecular
weight and a higher melt index, extrusion downstream is difficult to control. A further
problem with using recycled polyolefins is that it can be difficult to obtain the exact
type of polyolefins required and more often than not only recycled polyolefins such as
lower molecular weight and low density recycled polyolefins which are not particularly
suitable for wood-polyolefin composites are available. One particular type of
unsuitable polyolefin is linear low density polyethylene made initially for blown film
use. As this type of polyolefin is both low molecular weight and low density, it has a
very low creep resistance and therefore is unsuitable for wood-polyolefin composites.
An obvious solution to this problem would be to use virgin polyolefins only and in
particular virgin polyolefins having a high molecular weight. The disadvantage of this
solution however would be that these polyolefins are costly and difficult to process and
therefore their use in wood-polyolefin composites would not be cost effective.
Another solution to this problem is to add agents during the processing of the wood-
polyolefin composites to reduce creep. US Patent Publication No. US2004/0204519
discloses a wood-filled thermoplastic composite for use in the decking industry. A
number of additives are added during processing to reduce creep. These additives
include coupling agents such as chlorinated paraffin waxes and lubricants such as
ethylene bis-stearamide, stearate esters or fatty acid esters to increase the bond
strength and improve the processing of the composites. One of the drawbacks of this
thermoplastic composite and its process for preparation is that due to the amount of
additives required and the cost of these additives, the overall cost of preparing the
thermoplastic composite can exceed the value of the final product. Thus in order to
reduce cost, cheaper processing aids which are not as effective sometimes have to
be used.
A further disadvantage of these thermoplastic composites is that they do not take into
account the variability of the starting materials such as the polyolefins. This can lead
to excessive amounts of processing aids being used when not required, or insufficient
amounts being used when needed.
Thus there is a need for a process for preparing a wood-polyolefin composite
comprising at least a portion of recycled polyolefin and which has a higher resistance
to creep, but which can be prepared at minimum cost.
Statements of Invention
According to the invention, there is provided a process for preparing a wood—polyo|efin
composite having reduced creep; the composite comprising a cellulose-based filler in
the amount of between 20% and 80% by weight, a polyolefin in the amount of
between 80% and 20% by weight wherein at least 25% of the polyolefin is recycled
polyolefin and an amount of creep reducing agent;
characterised in that the process comprises:
preparing a sample wood-polyolefin composite by compounding an amount of
polyolefin and cellulose-based filler in a ratio corresponding to the amount of
polyolefin and cellulose—based filler in the wood-polyolefin composite and at a
temperature above the melting temperature of the polyolefin to form the
sample wood-polyoiefin composite;
analysing the sample wood-polyolefin composite;
detennining the amount and type of creep reducing agent required to reduce
creep in the wood-polyolefin composite; and
compounding the cellulose—based filler and polyolefin with the determined
amount of creep reducing agent in an extruder at a temperature above the
melting point of the polyolefin to form the wood-polyolefin composite.
The advantage of preparing a sample wood-polyolefin composite and analysing the
sample composite in order to determine the amount and type of creep reducing agent
required is that the most effective amount and type of creep reducing agent can be
chosen.
Each of the different types of creep reducing agents has different levels of
effectiveness. Thus different amounts of each of the agents can produce the same
effect. Furthermore the difference in cost between each of the creep reducing agents
is substantial. By determining the level of creep that would be present in the wood-
polyolefin composite, based on the level of creep in the sample wood-polyolefin
composite it is now possible to determine what the most effective creep reducing
agent would be at the lowest cost. As the correct amount and type of creep reducing
agent or agents can be more accurately determined, a sufficient but not excessive
amount of creep reducing agent can be added to prepare the final wood-polyolefin
composite, and thus the overall cost will be reduced.
Preferably, analysing the sample wood-polyolefin composite comprises:
measuring one or more of flexural modulus, flexural strength and creep of the
sample wood-polyolefin composite to yield one or more of a flexural modulus
value, a flexural strength value and a creep value.
Further preferably, determining the amount and type of creep reducing agent required
comprises the steps of:
comparing the or each measured flexural modulus value, flexural strength
value and creep value with a corresponding acceptable value; and
calculating the amount and type of creep reducing agent required based on
the or each value.
The advantage of measuring either or both of the flexural modulus and flex strength is
that they can be measured directly after preparation of the sample and thus the
amount of creep reducing agent required can be determined in less time. The
advantage of measuring the flexural modulus is that it is easier to measure than
flexural strength when the sample wood-polyolefin composites are in thin sections.
The advantage of measuring the creep directly is that the exact creep performance
can be determined and thus this is the most accurate analysis. The advantage of
measuring more than one of the flexural modulus, flexural strength and creep is that
more exact results can be obtained.
In one embodiment of the invention, the creep reducing agent is a silane grafted
polyolefin. in another embodiment of the invention, the creep reducing agent is a
mixture of silane and peroxide which grafts the polyolefin to form a silane grafted
polyolefin during compounding.
In a further embodiment of the invention, the creep reducing agent is a high molecular
weight polyolefin selected from the group consisting of one or more of ultra high
molecular weight polyethylene (UHMPE) and high molecular weight polyethylene
(HMWPE). In a still further embodiment of the invention, the creep reducing agent is a
long chain branched polyolefin. The advantage of using either high molecular weight
polyolefin or long chain branched polyolefin is that a substantial portion of this can be
obtained from recycled sources and thus can be obtained at a low cost.
In another embodiment of the invention, the creep reducing agent is a maleic
anhydride grafted polyolefin. The advantage of using this type of polyolefin is that it
has been found to be the most effective type of creep reducing agent and thus lower
amounts are required to achieve the same effect as other creep reducing agents.
In a further embodiment of the invention, the creep reducing agent is a natural or
synthetic silicate modified nanoclay selected from the group consisting of one or more
of montmorillonite, saponite, beidellite, nontronite, hectorite, bentonite and synthetic
fluoromica or any analogue thereof. in one embodiment prior to adding the nanoclay
to the polyolefin, preparing a masterbatch by adding between 10% and 50% of the
modified nanoclay by weight to between 50% and 90% of a masterbatch polyolefin by
weight of the masterbatch; and
adding the masterbatch in the amount of between 5% and 40% by weight to
the polyolefin and the cellulose-based filler to provide the wood-polyolefin
composite.
Preferably, the masterbatoh polyolefin is grafted with at least one monomer which is
capable of reacting with the polyolefin in a molten condition. In one embodiment of
this invention, the masterbatoh polyolefin is grafted prior to adding the nanoclay to the
masterbatoh polyolefin. In another embodiment of this invention, the nanoclay is
added to the masterbatoh poiyolefin during grafting of the masterbatoh poiyolefin.
Ideally, the masterbatoh poiyolefin is a recycled poiyolefin.
Preferably, the cellulose-based filler is selected from the group comprising one or
more of hardwoods, softwoods, plywood, peanut hull, bamboo, straw, ground up chip
board, ground up medium density fibre board, and cardboard.
l n one embodiment of the invention, the polyolefin is homopolymeric poiyolefin
selected from the group consisting of one or more of polyethylene and polypropylene.
Preferably, the polyethylene is selected from the group consisting of one or more of
High Density Polyethylene (HDPE), Medium Density Polyethylene (MDPE), Low
Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Low Density
Low Molecular Weight Polyethylene (LDLMWPE).
In another embodiment of the invention, the polyolefin is copolymeric polyolefin
selected from the group consisting of one or more of recycled butene-1, recycled
hexene-1, and recycled 4 methylpentene-1 (4MP-1).
Preferably, the molecular weight of the polyolefin is in the region of between 50,000
and 350.000 daltons.
The invention also relates to a wood-polyolefin composite prepared by the process
of the invention.
According to the invention, there is also provided a process for preparing a wood~
polyolefin composite article, comprising extruding the wood-poiyolefin composite of
the invention at a temperature in the region of between 150°C and 240°C to
form the composite article. According to the invention, there is still further provided a
wood-polyolefin composite article prepared by the process of the invention
Detailed Description of the Invention
The invention will now be more clearly understood from the following description of
some embodiments thereof given by way of example only with reference to the
figures, wherein:
Figure 1 outlines in flow diagram form the process according to the invention;
Figure 2 depicts the displacement of HMWtPE. HMWtPE. LLDPE and MMWtPE
as described in the Example;
Figure 3 depicts the displacement of LLDPE, LLDPE + HMWtPE, LLDPE + clay
and LLDPE + MAgPE as described in the Example; and
Figure 4 depicts the displacement of MMWtPE, MMWtPE + HMWtPE, MMWtPE
+ MAgPE, and MMWtPE + silane as described in the Example.
All of the equipment used is well known equipment and accordingly does not require
any further description.
Referring to Fig. 1 in step 1 a sample of polyolefin comprising a portion of recycled
polyolefin is obtained. In step 2, a sample of cellulose-based filler is obtained and is
compounded with the sample polyolefin in step 3 at a temperature above the melting
temperature of the polyolefin to form a sample wood-polyolefin composite in step 4.
The sample wood-polyolefin composite is analysed in step 5 and the amount and
type of creep reducing agent required to reduce creep in the wood-polyolefin
composite is determined in step 6. in step 7, the determined amount of creep
reducing agent is added to a further portion of polyolefin in step 8 and cellulose-
based filler in step 9 in an extruder where they are compounded in step 10 at a
temperature above the melting point of the polyolefin to form the wood-polyolefin
composite in step 11.
Preparation and analysis of sample wood-polyolefin composite
The sample wood-polyolefin composite is made up by compounding an amount of
polyolefin and cellulose-based filler in the same ratio as the amounts used to make
up the wood-polyolefin composite. The type of polyolefin used in the sample wood-
polyolefin composite will be the same as that which will be used to make up the
wood-polyolefin composite. As the sample will preferably be small, the compounding
of the test samples can be carried out using a lab Brabender mixer or other suitable
mixing equipment such as a small extruder. It will be appreciated however that if
larger amounts are used compounding could also be carried out in a manufacturing
extruder.
Analysis of the sample wood-polyolefin composite may be carried out by measuring
one or more of the flexural modulus, flexural strength and creep of the sample wood-
polyolefin composite. The flexural modulus and flexural strength are measured
according to the protocols laid out in the American Society for Testing Materials
(ASTM) tests under lSO1'/'8.
The creep is measured by hanging a weight from the sample wood-polyolefin
composite for a period of time and measuring the displacement of the composite over
time, as outlined in the accompanying example.
An acceptable flexural modulus value would be any value greater than 2.0GPa and
any value greater then 22MPa would be considered acceptable for flexural strength.
An acceptable value for creep would be a displacement of less than 9mm in 1000
hours.
It has been found that if the measured flexural modulus of the sample wood-
polyolefin composite is between 1.8GPa and 2.0GPa or the flexural strength is
between 18MPa and 22MPa that this will result in a slightly higher level of creep in
the final wood-polyolefin composite that would normally be acceptable for wood
replacement uses. All of the following creep reducing agents have been found to be
suitable to reduce creep in the final wood-polyolefin composite, if it is present at this
level in the sample composite.
All of the percentages expressed below are by weight of the polyolefin used to make
the wood-polyolefin composite.
Silane grafted polyolefin: 2% - 50%
High molecular weight polyolefin: 20% - 50%
Long chain branched polyolefin: 0.5% - 5%
Maleic anhydride grafted polyolefin: 1% - 2%
Modified nanoclay: 1% - 5%
Each of these creep reducing agents can work independently or in combination. It
will be appreciated that if any of these agents are combined that amounts at the lower
end of the ranges given can be used.
It has been found that the best combination when the creep is at this level in the
sample composite is a combination of the high molecular weight polyolefin and the
maleic anhydride grafted polyolefin. Modified nanoclay could also be added to each
of these polyolefins either alone or in combination to further improve creep in the final
wood-polyolefin composite.
Another successful combination which has been found is the combination of high
molecular weight polyolefin, maleic anhydride grafted polyolefin and long chain
branched polyolefin.
It has been found that if the measured flexural modulus of the sample wood-
polyolefin composite is between 1.6GPa and 1.8GPa or the flexural strength is
between 14MPa and 18 MPa that this will result in a greater percentage of creep in
the final wood-polyolefin composite. In this case the following creep reducing agents
have been found to be most suitable when creep is present at this level in the sample
composite:
Silane grafted polyolefin: 2% - 50%
High molecular weight polyolefin: 35% — 50%
Long chain branched polyolefin: 0.5% - 5%
Maleic anhydride grafted polyolefin: 1% — 5%
Modified nanoclayr 1% — 5%
in this case it has been found that all of the above creep reducing agents with the
exception of maleic anhydride grafted polyolefin need to be combined with at least
one other creep reducing agent in order to reduce creep to an acceptable level.
Maleic anhydride grafted polyolefin is an extremely effective creep reducing agent
and if added on its own during processing of the final wood-polyolefin composite at
the higher end of the range specified can reduce creep sufficiently.
In addition to this the following combinations of the other creep reducing agents can
successfully reduce creep when the flexural modulus and or flexural strength values
are within these ranges:
% - 5% silane grafted polyolefin, 35% - 50% high molecular weight polyolefin and/or
0.5% - 2% long chain branched polyolefin
% - 50% high molecular weight polyolefin, 1% — 2% maleic anhydride grafted
polyethylene and/or 0.5% - 5% long chain branched polyolefin
% - 5% modified nanoclay, 35% - 50% high molecular weight polyolefin and/or 0.5%
- 5% long chain branched polyolefin
It has been found that if the measured flexural modulus of the sample wood-
polyolefin composite is below 1.6GPa and the flexural strength is less than 14MPa
that this will result in an even greater percentage of creep in the final wood-polyolefin
composite. In this case the following creep reducing agents in the following amounts
have been found to be most suitable when creep is present at this level in the sample
composite:
Silane grafted polyolefin: 2% - 50%
High molecular weight polyolefin: 20% - 50%
Long chain branched polyolefin: 0.5% — 5%
Maleic anhydride grafted polyolefin: 1% - 5%
Modified nanoclay: 2% - 5%
In the above case, it has been found that each of the creep reducing agents must be
combined with at least one of the other creep reducing agents in order to reduce
creep in the final wood-polyolefin composite. The most successful combination has
been found to be the following:
% - 55% high molecular weight polyolefin, 2.5% - 7.5% maleic anhydride grafted
polyolefin and 0.5% - 1.5% long chain branched polyolefin.
The sample wood-polyolefin composite used for analysis can be of any size provided
that sufficient test pieces can be cut out for the flexural or creep tests, depending on
which test or tests are used.
Preparation of wood-polyolefin composite
It will be appreciated that the addition of each of the polyolefin, cellulose-based filler
and creep reducing agent to the extruder to form the wood-polyolefin composite can
be in any order.
Optionally, additives such as adhesion promoters, biocides, antioxidants, pigments,
processing aids, colorants, coupling agents, reinforcing agents, foaming agents and
lubricants can also be added to extruder. These additives can either be added at the
same time as the cellulose-based filler, polyolefin and creep reducing agent or some
time afterwards during compounding.
The cellulose-based filler may be wood flour, fibres or particles obtained from a
number of sources such as a lumber yard or furniture factory. Hardwoods, softwoods
and plywoods can be used, however hardwood is preferable. It is also possible to
use wood fibre particles from other sources such as peanut hull, bamboo and straw.
Other cellulose containing materials such as ground up chip board, ground up
medium density fibre board, and cardboard can also be used. Prior to compounding
with the polyolefin and creep reducing agent, the cellulose-based filler generally
undergoes a size reduction step in a suitable means such as a hammer mill which
results in the filler having an average particle size of less than 100 mesh. The
targeted mesh size of the cellulose-based filler is dependent upon the end-use
application.
As at least a portion of the polyolefins used is recycled, they more often than not
comprise a mixture of polyolefins having different melting points. The polyolefin with
the highest melting point should have a melting point below 170°C. The melting point
of this polyolefin should be low enough so as not to require compounding or extrusion
temperatures sufficiently high so as to cause degradation of the cellulose-based filler.
The creep reducing agents added can either be silane grafted polyolefins, high
molecular weight polyolefins, long-chain branched polyolefins, maleic anhydride
grafted polyolefins or nanoclay either added directly or in the form of a masterbatch.
In the specification a high molecular weight polyolefin refers to a polyolefin having a
molecular weight of greater than 200,000 and a long chain branched polyolefin refers
to a low density polyolefin having a molecular weight in the region of between
100,000 and 150,000 with long side chain branching, wherein each branch has
greater than 10 carbons.
The presence of any of these creep reducing agents in the wood-polyolefin
composite provides a higher resistance to creep in the final composite and extruded
composite article. Other types of agents which have been shown to reduce creep
such as chlorinated resins and chlorinated paraffin waxes could also be used.
The nanoclay used should also have been modified by cation exchange with an alkyl
ammonium ion. The monomer used to graft the masterbatch polyolefin may be any
one of ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic
acids and anhydrides and mixtures thereof. The monomer used is generally maleic
anhydride and is in the amount of less than 2% by weight of the masterbatch
polyolefin.
Creep is defined by the following formula:
A(t) oc O’/E0 t"
where:
_13_
A is the amount of deformation
E0 is the short term modulus of the material
n is the time-dependency of subsequent deformation described by a power law,
Therefore the deformation of the material is inversely proportional to E0 and
proportional to the time under stress, 0, to the power index n. In order to reduce
creep therefore the short term modulus should either be increased and/or the time-
dependency index n should be decreased.
One way of increasing the short term modulus (E0) of the composite is to
incorporate reinforcements such as fibres or flakes made from stiff inorganic
materials such as glass or clay into the composite. Thus the addition of nanoclays
either directly or in the form of a masterbatch serves to increase the short term
modulus (E0) and thus reduce creep in the composite. The resultant composites
comprising nanoclay have been found to have a significant reduction in creep in
particular in the short term.
The time dependency (n) has been found to be influenced by the polymer structure
and in particular by the amorphous regions of a crystalline structure. Increasing the
crystallinity has been found to reduce the proportion of amorphous network which
leads to a reduction in the time dependency index (n). In order to increase the
crystallinity, it is known that the molecular weight and/or chain branching in the
polymer must be reduced. However, this reduction would lead to a composite
susceptible to creep as the polymeric chains would slip readily from the crystals and
through the amorphous regions. It has however been found that that by
crosslinking the polymeric chains and thus connecting the branches to other
molecules and forming a network structure that this will also lead to a reduction in
the time dependency index n with the resultant composite having minimal or no
creep.
Crosslinking can be achieved by adding a creep reducing agent in the form of
polyolefins which promote crosslinking. The polyolefins can be in the form of long
chain branched polyolefins which reduce creep due to their complex molecular
architecture, producing a more tangled network, which reduces the molecular
mobility of the polyolefins. The polyolefins can also be high molecular weight
polyolefins wherein between 10% and 30% of its molecules are greater than 106 in
molecular weight. UHMPEs generally have a molecular weight of greater than
500,000 daltons and HMWPEs generally have a molecular weight of between
200,000 and 500,000 daltons.
different lengths wherein the length of their molecules result in a similar effect to the
Both have a broad distribution of molecules at
long-chain branched polyolefins.
The maleic anhydride grafted polyolefins reduce creep by the maleic anhydride end
bonding to the cellulose-based filler and the polymeric chains of the polyolefin. This
results in a bridge forming between the polyolefin and the cellulose-based filler.
These bridges assist creep resistance by increasing the short term modulus of the
composite and by improving the time dependency by tying the polyolefin to the
cellulose-based filler.
It will be appreciated that adding either a nanoclay or a polyolefin which promotes
crosslinking or a maleic anhydride grafted polyolefin will lead to a reduction in
creep. It will further be appreciated however, that by adding both a combination of
two or more of a nanoclay, a polyolefin which promotes crosslinking, or a maleic
anhydride grafted polyolefin that a significantly higher reduction in creep will be
expected as the short term modulus (E0)will be increased and the time dependency
index (n) will be decreased. This will also result in a prolonged reduction in creep
over long periods.
The following example is given by way of illustration only and should not be construed
as limiting the subject matter of the invention.
Example 1
Materials:
Recycled polyethylene: The recycled polyethylene was from one of the following
sources:
A) High molecular weight mixed bottle grade polyethylene (HMWtPE) which had a
melt index of circa. 8.0 HLMI (High Load Melt Index) (21.6kg)
Flex modulus: 2.56 GPa, Flex strength: 26.9MPa
B) Medium molecular weight polyethylene (MMWtPE) which was obtained from
used green rotomoulded tanks.
Flex modulus: 1.35 GPa, Flex strength: 20.7MPa
C) Linear low density polyethylene (LLDPE) which was obtained from used LLDPE
film.
Flex modulus: 1.26 GPa, Flex strength: 13.8MPa
Virgin polyethylene: The virgin polyethylene was from one of the following
sources:
D) Commercially available High Molecular Weight Polyethylene (HMWtPE),
Lupolen 52612 High Density Polyethylene (HDPE) ex Bassel. This polyethylene
was a high molecular weight blow moulding grade of polyethylene which had a melt
index of circa 2.0 high load (21 .6kg)
Flex modulus: 2.57 GPa, Flex strength: 35.5MPa
E) Cellulose-based filler: The wood used was commercially available wood flour
dried to less than 5%.
Creep reducing agents:
F) Maleic anhydride grafted polyethylene: Fusbond MB10OD ex DuPont.
G) Nanoclay: The nanoclay used was clay masterbatch obtained from Crownstone
Limited.
H) Silane: Silane grafted polyethylene ex Micropol
The different formulations were made up using the above materials in the amounts
shown in Table 1.
Table 1: Formulations: (% parts by weight)
Run D A C B E G F H
HMWtPE HMWtPE LLDPE MMWtPE Wood Clay MAgPE Silane
D 50 50
A 50 50
C 50 50
B 50 50
C+D 40 30 30
C+G 44 44 12
C+F 47.5 47.5 5
(5%)
C+F 49.5 49.5 1
(1%)
B+D 20 30 50
B+F 45 50 5
(5%)
B+F 49 50 1
(1%)
B+H 30 50 20
Each of the formulations were added to a Brabender Plastograph EC at 180°C over a
period of 2 minutes. Each mix was then mixed for a further 8 minutes at 60 rpm. The
resultant mixes were then compression moulded to produce flat sheets circa 3.5mm
thick.
All of the samples (wood-polyolefin composites comprising creep reducing agents and
wood-polyolefin composites with no creep reducing agents) were then tested for creep
as follows. Samples were cut from the pressed plaques to give a strip of wood-
polyolefin composite approximately 25mm x 10mm x 3.5mm. These were then
conditioned by leaving in a room at 23°C for a day and then placed in a rig with
support only at the two ends. A weight of 150g was then hung from the middle of the
sample and the displacement or “sag” was measured over a period of time and these
results are illustrated in Figs 2 to 4.
Fig. 2 shows the creep of each of the polyolefin resins A, B, C and D. A creep of over
9mm at 1000 hrs on this creep test predicts that products made from this material are
likely to have unacceptable creep in practice. Figs. 3 and 4 show the effect of various
creep reducing agents.
In this specification the terms “comprise, comprises, comprised and comprising” and
the terms “include, includes, included and including” are all deemed totally
interchangeable and should be afforded the widest possible interpretation.
The invention is not limited to the embodiments hereinbefore described which may be
varied in both construction and detail within the scope of the claims.
Claims (4)
1. A process for preparing a wood-polyolefin composite having reduced creep; the composite comprising a cellulose-based filler in the amount of between 20% and 80% by weight, a polyolefin in the amount of between 80% and 20% by weight wherein at least 25% of the polyolefin is recycled polyolefin and an amount of creep reducing agent; characterised in that the process comprises: preparing a sample wood-polyolefin composite by compounding an amount of polyolefin and cellulose-based filler in a ratio corresponding to the amount of polyolefin and cellulose-based filler in the wood- polyolefin composite and at a temperature above the melting temperature of the polyolefin to form the sample wood-polyolefin composite; analysing the sample wood-polyolefin composite; determining the amount and type of creep reducing agent required to reduce creep in the wood-polyolefin composite; and compounding the cellulose-based filler and polyolefin with the determined amount of creep reducing agent in an extruder at a temperature above the melting point of the polyolefin to form the wood- polyolefin composite.
2. A process for preparing a wood~polyo|efin composite substantially as described hereinbefore with reference to the accompanying example and drawings.
3. A wood-polyolefin composite as prepared by the process as claimed in any of claims 1 or 2. A process for preparing a wood-polyolefin composite article, comprising extruding the wood-polyolefin composite as claimed in claim 3 at a temperature in the region of between 150°C and 240°C to form the composite article. A wood-polyolefin composite article prepared by the process as claimed in claim
4.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IEIRELAND20/12/2005S2005/0848 |
Publications (1)
Publication Number | Publication Date |
---|---|
IES84698Y1 true IES84698Y1 (en) | 2007-10-03 |
Family
ID=
Similar Documents
Publication | Publication Date | Title |
---|---|---|
IE20060931A1 (en) | A process for preparing a wood-polyolefin composite | |
CA3019609C (en) | Cellulosic composites comprising wood pulp | |
US7041716B2 (en) | Cellulose filled thermoplastic composites | |
US7781500B2 (en) | Coupling agents for natural fiber-filled polyolefins | |
CN104204073B (en) | By the long fiber thermoplastics recycled and reproducible composition is formed | |
CN107722448B (en) | Composite composition for automotive interior material using natural fiber | |
EP2976381B1 (en) | Bamboo fibers reinforced polypropylene compositions | |
US7875667B2 (en) | Long-fiber reinforced polyolefin composition | |
US20080161526A1 (en) | Cross-Linked Polyethylene Resin for Large Part Blow Molding | |
JP2023546176A (en) | Polyolefin compositions containing polypropylene homopolymers and recycled plastic materials | |
US20140336327A1 (en) | Polyolefin masterbatch based on grafted polypropylene and metallocene catalyzed polypropylene | |
EP1357144B1 (en) | Polypropylene compositions | |
González-Sánchez et al. | Enhancement of mechanical properties of waste-sourced biocomposites through peroxide induced crosslinking | |
IES84698Y1 (en) | A process for preparing a wood-polyolefin composite | |
CA2435129C (en) | Cellulose filled thermoplastic composites | |
KR102099774B1 (en) | Functional material composition of film for rubber product packaging and method of producing the same | |
KR20110066745A (en) | Resin composition including high melt strength polyolefin | |
KR100920513B1 (en) | Polyethylene Composite for High- Pressure Pipes | |
CA2012944A1 (en) | Fiber-reinforced chlorinated polyethylene composition and process for production thereof | |
KR101428935B1 (en) | Blend of wood plastic composite and windows made from thereof | |
KR20200065338A (en) | A fiber reinforced composite resin composition | |
CN114957831A (en) | HDPE composite material for inner layer of automobile plastic oil tank and preparation method thereof | |
KR20240046618A (en) | Polyolefin composition comprising polyethylene and recycled plastic materials | |
Hemmasi et al. | LOW DENSITY POLYETHYLENE | |
KR20040089207A (en) | Polyethylene Composite for Pipes with High ESCR |