WO2007071732A1 - Procede pour preparer un composite de bois-polyolefine - Google Patents

Procede pour preparer un composite de bois-polyolefine Download PDF

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Publication number
WO2007071732A1
WO2007071732A1 PCT/EP2006/070014 EP2006070014W WO2007071732A1 WO 2007071732 A1 WO2007071732 A1 WO 2007071732A1 EP 2006070014 W EP2006070014 W EP 2006070014W WO 2007071732 A1 WO2007071732 A1 WO 2007071732A1
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Prior art keywords
polyolefin
wood
composite
preparing
creep
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PCT/EP2006/070014
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English (en)
Inventor
Andrew Burns
Alec Milligan
Robert Meek
Maura Burke
Edward Quentin Clutton
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Crownstone Limited
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Filing date
Publication date
Application filed by Crownstone Limited filed Critical Crownstone Limited
Priority to EP06841514A priority Critical patent/EP1963421A1/fr
Publication of WO2007071732A1 publication Critical patent/WO2007071732A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2397/00—Characterised by the use of lignin-containing materials
    • C08J2397/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials

Definitions

  • the present invention relates to a process for preparing a wood-po!yolefin composite having reduced creep; the composite comprising a celiulose-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 polyofefin is recycled polyolefin and an amount of creep reducing agent.
  • the invention also relates to a process for preparing a wood-pofyolefin 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.
  • cellulose- based filler refers to all types of material containing cellulose and includes but is not limited to wood fiour, fibre and particles and other natural materials.
  • a polyolefin is a polymer of the alkene family of hydrocarbons.
  • by weight refers to by weight of the wood-polyo!efin 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.
  • 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 poiyolefins which are not particularly suitable for wood-polyolefin composites are available.
  • polystyrene resin made initially for blown film use.
  • polyolefin is both low molecular weight and low density, it has a very low creep resistance and therefore is unsuitable for wood-polyolefin composites.
  • thermoplastic composites 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.
  • a process for preparing a wood-polyolefin composite having reduced creep 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;
  • 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-polyolefjn composite and at a temperature above the melting temperature of the polyolefin to form the sample 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.
  • the difference in cost between each of the creep reducing agents is substantial.
  • analysing the sample wood-polyolefin composite comprises:
  • determining the amount and type of creep reducing agent required comprises the steps of:
  • the advantage of measuring either or both of the flexura! 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.
  • the creep reducing agent is a silane grafted polyolefin.
  • the creep reducing agent is a mixture of silane and peroxide which grafts the polyolefin to form a silane grafted polyolefin during compounding.
  • 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).
  • UHMPE ultra high molecular weight polyethylene
  • HMWPE high molecular weight polyethylene
  • the creep reducing agent is a long chain branched polyolefin.
  • 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.
  • the creep reducing agent is a natural or synthetic silicate modified nanoclay selected from the group consisting of one or more of montmoriilonite, saponite, beidellite, nontronite, hectorite, bentonite and synthetic fluoromica or any analogue thereof.
  • preparing a masterbatch by adding between 10% and 50% of the modified nanoclay by weight to between 50% and 90% of a masterbatch polyoiefin by weight of the masterbatch; and
  • the masterbatch polyolefi ⁇ is grafted with at least one monomer which is capable of reacting with the polyolefin in a molten condition.
  • the masterbatch polyolefin is grafted prior to adding the nanoclay to the masterbatch polyolefin.
  • the nanoclay is added to the masterbatch polyolefin during grafting of the masterbatch polyolefin.
  • the masterbatch polyolefin is a recycled polyolefin.
  • 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.
  • the polyolefin is homopolymeric polyolefin selected from the group consisting of one or more of polyethylene and polypropylene.
  • 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).
  • 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 ).
  • 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.
  • a process for preparing a wood- polyolefin composite article comprising extruding the wood-polyolefin composite of the invention at a temperature in the region of between 15O°C and 24O 0 C to form the composite article.
  • a wood-polyolefin composite article prepared by the process of the invention - 1 -
  • 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;
  • Figure 4 depicts the displacement of MMWtPE, MMWtPE + HMWtPE, MMWtPE + MAgPE, and MMWtPE + silane as described in the Example.
  • step 1 a sample of polyolefin comprising a portion of recycled polyolefin is obtained.
  • 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.
  • step 5 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-poiyolefin composite is determined in step 6.
  • 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.
  • the sample wood-polyolefin composite is made up by compounding an amount of polyolefin and cellulose-based filier 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.
  • 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 ISO178.
  • 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.
  • 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.
  • 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 nanoclay: 1% - 5%
  • 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.
  • Silane grafted polyolefin 2% - 50%
  • 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.
  • 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.
  • 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.
  • a size reduction step 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.
  • the polyolefins used are 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 0 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, mateic anhydride grafted polyolefins or nanociay either added directly or in the form of a masterbatch.
  • 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.
  • 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 nanociay used should also have been modified by cation exchange with an alky! 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:
  • E 0 is the short term modulus of the material n is the time-dependency of subsequent deformation described by a power law
  • the deformation of the material is inversely proportional to Eo and proportional to the time under stress, ⁇ , to the power index n.
  • 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 (E 0 ) 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.
  • reinforcements such as fibres or flakes made from stiff inorganic materials such as glass or clay
  • nanoclays either directly or in the form of a masterbatch serves to increase the short term modulus (E 0 ) 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 10 6 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. Both have a broad distribution of molecules at different lengths wherein the length of their molecules result in a similar effect to the 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 polyoiefin 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.
  • 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
  • HMWtPE High molecular weight mixed bottle grade polyethylene
  • HLMI High Load Melt index
  • Flex modulus 2.56 GPa
  • Flex strength 26.9MPa
  • MMWtPE Medium molecular weight polyethylene
  • LLDPE Linear low density polyethylene
  • Virgin polyethylene The virgin polyethylene was from one of the following sources:
  • HMWtPE High Molecular Weight Polyethylene
  • HDPE High Density Polyethylene
  • E) Cellulose-based filler The wood used was commercially available wood flour dried to less than 5%.
  • Creep reducing agents
  • Nanoclay The nanoclay used was clay masterbatch obtained from Crow ⁇ stone Limited.
  • Each of the formulations were added to a Brabender Plastograph EC at 18O 0 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.
  • Fig. 2 shows the creep of each of the poiyolefin resins A, B 1 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.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé pour préparer un matériau bois-polyoléfine composite, à fluage réduit, comprenant entre 20 et 80 % en poids d'une charge à base de cellulose, entre 80 et 20 % en poids de polyoléfine, au moins 25 % de la polyoléfine étant une polyoléfine recyclée, ainsi qu'un agent de réduction du fluage. L'invention concerne également un procédé de préparation d'un article en matériau composite, le matériau bois-polyoléfine composite, ainsi que ledit article en matériau composite ainsi obtenu.
PCT/EP2006/070014 2005-12-20 2006-12-20 Procede pour preparer un composite de bois-polyolefine WO2007071732A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06841514A EP1963421A1 (fr) 2005-12-20 2006-12-20 Procede pour preparer un composite de bois-polyolefine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IES2005/0848 2005-12-20
IE20050848 2005-12-20

Publications (1)

Publication Number Publication Date
WO2007071732A1 true WO2007071732A1 (fr) 2007-06-28

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EP (1) EP1963421A1 (fr)
IE (2) IES20060932A2 (fr)
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CN101880464A (zh) * 2010-07-12 2010-11-10 安徽农业大学 一种竹基/热塑性塑料纳米复合材料
CN108530747A (zh) * 2018-04-16 2018-09-14 合肥欧克斯新型建材有限公司 一种聚丙烯-改性蒙脱土纳米复合材料的制备工艺
CN109517248A (zh) * 2018-11-21 2019-03-26 常宁市广富木业有限公司 高韧性木塑复合板材组合物及其制备方法
CN109749194A (zh) * 2018-12-20 2019-05-14 上海昶法新材料有限公司 一种增强型pe木塑复合型材及其制备方法
WO2019152829A1 (fr) 2018-02-01 2019-08-08 Dow Silicones Corporation Composition, article composite polymère formé avec celle-ci et procédé pour sa préparation
US11312861B2 (en) 2019-08-07 2022-04-26 Dow Silicones Corporation Solid carrier component including a liquid polyorganosiloxane and methods for preparation and use of the solid carrier component
US11312862B2 (en) 2019-08-07 2022-04-26 Dow Silicones Corporation Solid carrier component including a liquid polydiorganosiloxane and methods for preparation and use of the solid carrier component
US11377561B2 (en) 2019-08-07 2022-07-05 Dow Silicones Corporation Alkenyl-functional polydiorganosiloxane compositions and methods for use thereof in forming wood plastic composites
WO2023038856A1 (fr) 2021-09-08 2023-03-16 Greentech Composites Llc Composite thermoplastique non polaire présentant une image imprimée par sublimation de colorant et procédé permettant de les former
US11820898B2 (en) 2019-08-07 2023-11-21 Dow Silicones Corporation Polydiorganosiloxane compositions and methods for use thereof in forming wood plastic composites

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CN101880464A (zh) * 2010-07-12 2010-11-10 安徽农业大学 一种竹基/热塑性塑料纳米复合材料
US11884821B2 (en) 2018-02-01 2024-01-30 Dow Silicones Corporation Composition, polymer composite article formed therewith, and method of preparing same
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CN109517248A (zh) * 2018-11-21 2019-03-26 常宁市广富木业有限公司 高韧性木塑复合板材组合物及其制备方法
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WO2023038856A1 (fr) 2021-09-08 2023-03-16 Greentech Composites Llc Composite thermoplastique non polaire présentant une image imprimée par sublimation de colorant et procédé permettant de les former

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