CN1513918A - Wood plastic composite material and its preparation method and application - Google Patents

Wood plastic composite material and its preparation method and application Download PDF

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Publication number
CN1513918A
CN1513918A CNA021601232A CN02160123A CN1513918A CN 1513918 A CN1513918 A CN 1513918A CN A021601232 A CNA021601232 A CN A021601232A CN 02160123 A CN02160123 A CN 02160123A CN 1513918 A CN1513918 A CN 1513918A
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plastic composite
plastics
wood plastic
wood
weight
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CNA021601232A
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CN1219000C (en
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张国立
胡孝义
陈志达
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中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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Abstract

A wood-plastics composition is prepared from used or waste plastics, wooden fibres for modifying plastics, and resin compatibilizer through fusing and proportionally mixing. Said resin compatibilizer is prepared from EVA, acrylic acid or acrylate and polyvinyl chloride through mixing. Its advantages are high strength toughness, and improved machinability.

Description

A kind of wood plastic composite and its production and application

Technical field

The present invention relates to a kind of plastics composite, further, relate to a kind of by wood fibre with reclaim matrix material that plastic blend forms and its production and application.

Background technology

Wood plastic composite can be widely used in industries such as packing, building, compares with timber, also has easy processing, intensity height, anticorrosion, insect protected, damp proof, long service life, advantage such as can reuse.

Utilize the filling-modified plastics of wood fibre, abroad possess some special knowledge, " liking because of wood " famous as Japan is exactly this series products, and moral company of Canadian association has also developed and similarly moulded woodwork (employing is extruded or the pressing process moulding); Austria Cincinnati company and PPT mould enterprise are also developed various sheet materials and are moulded woodwork.Domestic research about this also launches, and the enterprise in Tangshan plastic institute, the National University of Defense technology, Guangdong University of Technology, Beijing University of Chemical Technology, Beijing Automobile Workshop Feitian and Wuxi, Hangzhou, Mengcheng has carried out the research of wood plastic composite and processing units.

Though in the prior art wood plastic composite is had the research in some early stages, the bottleneck problem of wood plastic composite is performance, the extruded velocity of wood plastic composite and the very difficult solutions such as adaptability of wood plastic composite expressing technique of wood plastic composite for example.The material that the particularly high share of wood plastic composite is filled because the consistency between wooden and the plastics is bad, generally all causes the low shortcoming of composite property; And, be easy to generate processing problems because the rheological characteristics of wood plastic composite uniqueness and the difficulty of conducting heat cause the extruded velocity of wood plastic product very slow.

Along with development of global economy, on the one hand, the use that various plastics are a large amount of, waste or used plastics rubbish spreads all over the world, and the environment of human living has been caused great pollution; On the other hand, a large amount of forests is cut down, and has caused the destruction of soil erosion and ecotope.How solving white pollution, saving the forest reserves is pendulum big problems in face of people.Wood fibre or vegetable fibre are filled the plastics that reclaim, through custom-built machine extrude, compacting or injection moulding, the goods of making can substitute timber-work, have both solved white pollution problems, have saved the forest reserves again, help the protection of ecotope.

Therefore from environmental protection and economic angle, it is more considerable to use wood fibre to fill the meaning and the prospect of waste or used plastics, but because the characteristics that mix of waste or used plastics, causes the production process of this kind wood plastic composite and quality product is easier fluctuates.

The patent No. is the Japanese Patent of JP 57187392, provides a kind of by cross-linked polyolefin chip and wood chip and tamanori blend and the wood fibre filled plastics fuel that obtains.Its objective is in order to make polyolefine reclaimed materials and waste wood can be used as fuel feedback.Employed tamanori can be selected from cumarone resin, terpine resin and lower molecular weight isoprene-isobutylene rubber etc., and this invention can be made into the effigurate fuel that transports and use be convenient to.This kind plastic fuel need not that the processibility of the composition machine performance of material and extrusion moulding is had requirement.

Publication number provides a kind of by wood powder enhanced compound plastic plate for the Chinese patent application of CN 1255427A.Be polypropylene, a small amount of polyethylene and wood powder, paper scrap and hotmelt melt blending are extruded or to be rolled and get.So-called hotmelt is the grafts of polypropylene and polar monomer (as MALEIC ANHYDRIDE etc.).The recovery plastics are not used in this patent application, and adding wood powder in plastics is in order to improve the intensity of plastic plate.Wherein the acquisition of hotmelt also needs graft process in advance, and preparation method and operating procedure are complicated, the cost height.Publication number also provides similar a kind of matrix material by wood powder reinforced polypropylene for the Chinese patent application of CN 1257890A.Also use polyacrylic grafts as wood powder and polyacrylic coupling agent.Add conventional processing aid in addition, be selected from polyethylene wax, chlorinatedpolyethylene, oxidic polyethylene, its chlorinated polypropylene, the clorafin one or more, to improve the flowability of wood powder.

Publication number provides the blend of a kind of wood fibre and waste or used plastics for the Chinese patent application of CN 1204656A.Oligomer polymer overmold wood powder is used in this invention, improves the avidity of wood powder and waste or used plastics.The oligomer polymkeric substance is selected from ethene paraffin or Atactic Polypropelene or chlorinatedpolyethylene.This patent does not provide the composition machine performance of relevant matrix material and the data of processing characteristics.

Summary of the invention

The contriver considers environmental protection and economic dispatch factor, utilizes wood fibre and waste and old recovery plastics to prepare matrix material.In order fully to recycle waste or used plastics, plastics used in the present invention are for reclaiming plastics or its mixture, and therefore preparing this kind matrix material not only faces the problem that runs in the above-mentioned prior art, also exists the problem of consistency difference between the waste or used plastics.In order to address these problems, the contriver does a large amount of research and improvement to the prescription of wood plastic composite, improve the auxiliary agent of consistency between plastics and plastics, plastics and the wood fibre by adding, can not only improve the mechanical property of material, can also improve the adaptability of processing characteristics and processing.Make wood plastic composite of the present invention not only improving greatly aspect intensity and the toughness, in molding process, rate of extrusion improves more than 50% at least.The production efficiency and the application prospect of wood plastic composite have been improved greatly.

The invention provides a kind of wood plastic composite of filling the remodeling waste or used plastics by wood fibre;

The present invention also provides the preparation method of this wood plastic composite;

In addition, the present invention further provides the purposes of this kind wood plastic composite.

A kind of wood plastic composite of the present invention includes following component:

A. plastics;

B. wood fibre;

C. resin compatible agent.

The ratio of weight and number of wood fibre and plastics is 100: 100~250: 100 in the above component; Wherein plastics are the reclaimed materials of thermoplastics, and this reclaimed materials is generally the mixture of multiple plastics.Recovery plastics of the present invention mainly comprise one or more of following material: polyethylene, polypropylene, polyvinyl chloride, polystyrene, third rare nitrile-butadiene-styrene terpolymer (ABS).These materials account for and reclaim more than 80% of plastics gross weight.

In the component of wood plastic composite of the present invention, add the resin compatible agent and can improve the consistency that reclaims between the plastics polycomponent, be beneficial to improve mechanical property and processing characteristics.The ratio of weight and number of resin compatible agent and plastics gross weight is 2: 100~15: 100, is preferably 5: 100~10: 100.The resin compatible agent is made up of the polymkeric substance of ethene-vinyl acetate copolymer (EVA), vinylformic acid or acrylate and chlorinatedpolyethylene three's mixture, wherein the EVA consumption is 20~80% of three's gross weight, and the polymkeric substance of vinylformic acid or acrylate and the weight ratio of chlorinatedpolyethylene are 1: 3~3: 1.The polymkeric substance of vinylformic acid or acrylate can be selected from: ethylene-acrylic acid copolymer (EAA), polyacrylic acid (PAA), butyl polyacrylate (PBA), polyethyl acrylate (PEA), polymethyl acrylic acid (PMAA), polymethyl acrylate (PMA) are preferably ethylene-acrylic acid copolymer (EAA).

Wood fibre of the present invention comprises the fiber after the cauline leaf, bar, kind shell of sawdust, wood powder and other Woody plant etc. pulverized.The median size of its fiber is preferably more than 20 orders, and water content is preferably below 5%.

Wood plastic composite of the present invention also comprises the adding reinforcing filler in its component.At this, reinforcing filler comprises common used filling additive in the modifying plastics processing, as lime carbonate, talcum powder etc., also comprises flyash and/or industrial slag etc., preferred powder coal ash and/or industrial slag.The median size of flyash and industrial slag should be 2~120 μ m, is preferably 2~30 μ m.Flyash and/or industrial slag be during as reinforcing filler, with the ratio of weight and number of plastics in the wood plastic composite be 5: 100~20: 100, be preferably 10: 100~15: 100.Utilize flyash and or industrial slag as the reinforcing filler of wood plastic composite, can improve hardness, the bending strength of wood plastic composite greatly.And, not only help environmental protection to the utilization of waste material of flyash and industrial slag, and can also reduce the cost of wood plastic composite greatly, be a very desirable measure of turning waste into wealth.

In addition, can also add some common processing aids in the wood plastic composite of the present invention, as terpine resin, lipid acid and its esters, white oil etc., as the wood fibre tackifier, can improve the tackiness of wood fibre, help the improvement of processibility, be beneficial to the material densification, the wood fibre uniform distribution.

Except can adding the wood fibre tackifier, the moistening agent of using usually in the consumption adding plastic working modification, tensio-active agent etc. improve the auxiliary agent of wood fibre surfactivity and processibility usually in the wood plastic composite.Wherein moistening agent comprises terephthalic acid second dioctyl ester (DOP) and whiteruss etc.Tensio-active agent comprises stearic acid compound, titanate coupling agent and silane coupling agent etc.

Remove the above,, in the component of wood plastic composite of the present invention, can also add the conventional auxiliary agent of plastic working in right amount, as oxidation inhibitor, toughner, fire retardant and whipping agent etc. according to the processing needs.

The preparation method of wood plastic composite of the present invention is that above-described component is comprised that plastics, wood fibre, resin compatible agent and wood fibre tackifier etc. make described wood plastic composite by common melt-mixing method in the plastic working.

Concrete grammar is that said components is carried out premix earlier by proportioning, and the equipment of use is mixing equipment used in the common plastic working, as high-speed mixer, kneader etc.Can look the material situation during premix and suitably heat, this mixing temperature generally should be lower than 100 ℃.Use general rubber plastic blend equipment to carry out melt blending the material behind the premix, obtain wood plastic composite of the present invention through step such as extruding pelletization again.The blending temperature of material is the general processing temperature of used plastics in the prescription, selects not only guaranteeing the complete fusion of matrix thermoplastics but also can not make in the scope of its decomposition, generally between 140~220 ℃.Most of plastics that reclaim are based on polyolefine, if the polymerized ethylene content height, it is more on the low side that blending temperature is wanted, between 140~160 ℃; If polypropylene content height, blending temperature want more higher, between 160~220 ℃.Blending equipment is the general blending equipment in the rubber and plastic processing industry, can be twin screw extruder, single screw extrusion machine, mill and Banbury mixer etc.

Wood plastic composite of the present invention, and the wood plastic composite that obtains by method of the present invention, can by as common plastic product forming methods such as hot-forming, injection moulding and extrusion moulding, and the goods of preparation wood plastic composite.These goods can comprise building materials, finishing material, foam material, sheet material, wrapping material, toy, auto parts etc.Can also be used to making wooden plastic well lid, sleeper, floor, road sign, Hua Chi etc. in addition.Also can be applied to shoe industry.

The advantage of wood plastic composite of the present invention is: have higher bending strength, hardness, wear-resisting and ageing-resistant performance.Hold concurrently and bear some performances of timber and thermoplastics.Can follow closely as this kind wood plastic composite and can dig and can saw, be easy to install, but at many occasion replacing woods; Simultaneously have thermoplasticity again, be easy to machine-shaping.In molding process, the rate of extrusion of wood plastic composite of the present invention improves more than 50% at least than normal wood moulding material.The production efficiency and the application prospect of wood plastic composite have been improved greatly.

Embodiment

Further describe the present invention below in conjunction with embodiment, scope of the present invention is not subjected to the restriction of these embodiment.Scope of the present invention proposes in claims.

In following examples, wood fibre is that particle diameter is 50 orders, the wood powder of moisture content 1.5%, and Furniture Factory provides by Beijing's the Temple of Heaven; EAA is produced by The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, (Dow Chemical), the trade mark 3310; Chlorinatedpolyethylene: trade mark CPE-36, chemical plant, Weifang, Shandong produces; EVA: trade mark 5-0.3, Beijing Organic Chemical Plant produces; Flyash is provided by Shoudu Iron and Steel Co power plant; All the other raw materials are the commercially available prod.

Embodiment 1

With wood powder, waste or used plastics (PP content reaches the above reclaimed materials of 80% weight), processing aid, compatilizer proportionally, mix in high speed agitator, mixing temperature is 100 ℃, high-speed stirring 5 minutes.A part of compound is adopted the ZSK-25 twin screw extruder blend granulation of German WP company, and each section of forcing machine temperature is respectively: 170 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃ and 180 ℃ (head temperature).The repressed method of pellet is made the standard batten, carries out every Mechanics Performance Testing.With another part compound, extrusion profile on homemade twin screw extruder uses universal mold, in order to the test extruded velocity.The screw zones temperature is 185/190/195/195 ℃, 185/185/1858/185 ℃ of each section of head temperature.Electric current 16.3A, torque 66%, extruded velocity: 1700mm/min.If do not add processing aid, speed has only about 1000mm/min, has added processing aid, and speed has improved 70%.Prescription, testing standard and result are as shown in table 1, and each component is all in parts by weight.

Embodiment 2~3

As the weighting agent, all the other components and condition are with embodiment 1 except that adding flyash (median size is 100 μ m).Through extruding pelletization, the repressed method of pellet is made the standard batten, carries out every Mechanics Performance Testing; Simultaneously also by extrusion moulding with the test extruded velocity.Prescription, testing standard and result are as shown in table 1, and each component is all in parts by weight.

Can see, add flyash, the socle girder notched Izod impact strength of material slightly descends, and flexural strength, bending elastic modulus and heat-drawn wire all are improved.

Embodiment 4

With wood powder, waste or used plastics (PE content reaches the above reclaimed materials of 80% weight), processing aid, compatilizer proportionally, mix in high speed agitator, mixing temperature is 90 ℃, high-speed stirring 5 minutes.A part of compound is adopted the ZSK-25 twin screw extruder blend granulation of German WP company, and each section of forcing machine temperature is respectively: 115 ℃, 130 ℃, 135 ℃, 135 ℃, 140 ℃ and 140 ℃ (head temperature).The repressed method of pellet is made the standard batten, carries out every Mechanics Performance Testing.With another part compound extrusion profile on homemade twin screw extruder, use universal mold, in order to the test extruded velocity.The screw zones temperature is 135/140/145/148 ℃, 148/148/148/148 ℃ of each section of head temperature.Electric current 15.2A, torque 63%, extruded velocity: 1320mm/min.If do not add compatilizer, speed has only about 800mm/min, has added processing aid, and speed has improved 60%.Prescription, testing standard and result are as shown in table 1, and each component is all in parts by weight.

Embodiment 5

With wood powder, waste or used plastics (polypropylene, polyethylene and polyvinyl chloride mixture content reach the reclaimed materials more than 80%), processing aid, resin compatible agent proportionally, mix in high speed agitator, mixing temperature is 90 ℃, high-speed stirring 5 minutes.A part of compound is adopted the ZSK-25 twin screw extruder blend granulation of German WP company, and each section of forcing machine temperature is respectively: 130 ℃, 150 ℃, 160 ℃, 160 ℃, 160 ℃ and 160 ℃ (head temperature).Pellet is made the standard batten through injection moulding, carries out every Mechanics Performance Testing.With another part compound extrusion profile on homemade twin screw extruder, use universal mold, in order to the test extruded velocity.The screw zones temperature is 165/170/175/175 ℃, 170/170/170/170 ℃ of each section of head temperature, electric current 16.6A, torque 61%, extruded velocity: 1510mm/min.If do not add compatilizer, speed has only about 900mm/min, has added processing aid, and speed has improved 70%.Prescription, testing standard and result are as shown in table 1, and each component is all in parts by weight.

Embodiment 6

With waste or used plastics (with embodiment 5), wood powder, processing aid, compatilizer proportionally, mix in high speed agitator, mixing temperature is 90 ℃, high-speed stirring 5 minutes.A part of compound is adopted the ZSK-25 twin screw extruder blend granulation of German WP company, and each section of forcing machine temperature is respectively: 130 ℃, 150 ℃, 160 ℃, 160 ℃, 160 ℃ and 160 ℃ (head temperature).Pellet is made the standard batten through injection moulding, carries out every Mechanics Performance Testing.With another part compound extrusion profile on homemade twin screw extruder, use universal mold, in order to the test extruded velocity.The screw zones temperature is 165/170/175/175 ℃, 170/170/170/170 ℃ of each section of head temperature, electric current 16.6A, torque 61%, extruded velocity: 1590mm/min.If do not add compatilizer, speed has only about 900mm/min, has added processing aid, and speed has improved 75%.Prescription, testing standard and result are as shown in table 1, and each component is all in parts by weight.

Embodiment 7

With waste or used plastics (with embodiment 5), wood powder, processing aid, compatilizer proportionally, mix in high speed agitator, mixing temperature is 90 ℃, high-speed stirring 5 minutes.A part of compound is adopted the ZSK-25 twin screw extruder blend granulation of German WP company, and each section of forcing machine temperature is respectively: 130 ℃, 150 ℃, 160 ℃, 160 ℃, 160 ℃ and 160 ℃ (head temperature).Pellet is made the standard batten through injection moulding, carries out every Mechanics Performance Testing.With another part compound extrusion profile on homemade twin screw extruder, use universal mold, in order to the test extruded velocity.The screw zones temperature is 165/170/175/175 ℃, 170/170/170/170 ℃ of each section of head temperature, electric current 16.6A, torque 61%, extruded velocity: 1010mm/min.Prescription, testing standard and result are as shown in table 1, and each component is all in parts by weight.

Comparative Examples 1

Except not adding the resin compatible agent, all the other components and condition are with embodiment 5.Through extruding pelletization, the repressed method of pellet is made the standard batten, carries out every Mechanics Performance Testing; Simultaneously also by extrusion moulding with the test extruded velocity.Prescription, testing standard and result are as shown in table 1, and each component is all in parts by weight.

Table 1 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Comparative Examples 1 Wood powder ??100 ??100 ??100 ??100 ??100 ??100 ??100 ??100 Plastics ??100 ??100 ??100 ??100 ??100 ??200 ??200 ??100 Compatilizer EVA ??3 ??3 ??3 ??3 ??6 ??1 ??5 ??0 EAA ??1 ??1 ??1 ??1 ??0.8 ??0.8 ??2 ??0 Chlorinatedpolyethylene ??1 ??1 ??1 ??1 ??1.2 ??0.8 ??1 ??0 Flyash ??0 ??10 ??20 ??0 ??0 ??0 ??0 ??0 Stearic acid ??1 ??1 ??1 ??1 ??1 ??2 ??2 ??1 Whiteruss ??1 ??1 ??1 ??1 ??1 ??2 ??2 ??1 Titanate coupling agent ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 Socle girder notched Izod impact strength (J/m) GB1843-93 ??48.9 ??43.9 ??30.2 ??57.0 ??65.3 ??60.1 ??51.3 ??58.2 Flexural strength (MPa) GB9341-88 ??28.1 ??32.1 ??34.1 ??13.4 ??17.2 ??18.3 ??19.2 ??13.8 Modulus in flexure (Mpa) GB9341-88 ??1921 ??2132 ??2210 ??753 ??1095 ??1185 ??1210 ??1025 Heat-drawn wire (℃) GB1634-79 ??153 ??154 ??154 ??62 ??85 ??86 ??86 ??82 Extruded velocity (mm/min) ??1700 ??1650 ??1630 ??1320 ??1510 ??1590 ??1010 ??900 Extruded velocity improves percentage (%) ??70 ??-- ??-- ??60 ??70 ??75 ??-- ??--

Claims (10)

1. wood plastic composite includes following component:
A. plastics;
B. wood fibre;
C. resin compatible agent;
The ratio of weight and number of wood fibre and plastics is 100: 100~250: 100 in the above component, and the ratio of weight and number of resin compatible agent and plastics is 2: 100~15: 100; Described resin compatible agent is made up of the polymkeric substance of ethene-vinyl acetate copolymer, vinylformic acid or acrylate and chlorinatedpolyethylene three's mixture, therein ethylene-vinyl acetate copolymer consumption is 20~80% of three's gross weight, and the polymkeric substance of vinylformic acid or acrylate and the weight ratio of chlorinatedpolyethylene are 1: 3~3: 1.
2. a kind of wood plastic composite according to claim 1 is characterized in that its particulate median size of described wood fibre is more than 20 orders, and water content is below 5%.
3. a kind of wood plastic composite according to claim 1 is characterized in that described plastics comprise one or more of following thermoplastics: polyethylene, polypropylene, polyvinyl chloride, polystyrene, third rare nitrile-butadiene-styrene terpolymer.
4. a kind of wood plastic composite according to claim 1, the ratio of weight and number that it is characterized in that described resin compatible agent and plastics is 5: 100~10: 100.
5. a kind of wood plastic composite according to claim 1 is characterized in that the polymkeric substance of vinylformic acid in the described resin compatible agent or acrylate is selected from ethylene-acrylic acid copolymer, polyacrylic acid, butyl polyacrylate, polyethyl acrylate, polymethyl acrylic acid, polymethyl acrylate.
6. a kind of wood plastic composite according to claim 1, it is characterized in that including reinforcing filler in the component of described wood plastic composite, reinforcing filler is made up of flyash and/or industrial slag, and the ratio of weight and number of itself and plastics is 5: 100~20: 100.
7. a kind of wood plastic composite according to claim 6, the ratio of weight and number that it is characterized in that described reinforcing filler and plastics is 10: 100~15: 100.
8. a kind of wood plastic composite according to claim 6, the median size that it is characterized in that described flyash or industrial slag are 2~120 μ m.
9. according to the preparation method of each described a kind of wood plastic composite of claim 1~8, it is characterized in that making described wood plastic composite in interior component by melt blending with comprising described plastics, wood fibre and resin compatible agent.
10. according to each described a kind of wood plastic composite of claim 1~8 and according to the prepared application of wood plastic composite on moulded products of claim 9.
CN 02160123 2002-12-31 2002-12-31 Wood plastic composite material and its preparation method and application CN1219000C (en)

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