CN102492239A - AM mixture used for wood plastic products, and preparation and application methods thereof - Google Patents
AM mixture used for wood plastic products, and preparation and application methods thereof Download PDFInfo
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- CN102492239A CN102492239A CN2011103888124A CN201110388812A CN102492239A CN 102492239 A CN102492239 A CN 102492239A CN 2011103888124 A CN2011103888124 A CN 2011103888124A CN 201110388812 A CN201110388812 A CN 201110388812A CN 102492239 A CN102492239 A CN 102492239A
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Abstract
The invention belongs to the field of chemical synthesis and specifically relates to an AM mixture used for wood plastic products and preparation and application methods thereof. The AM mixture is characterized in that the mixture is an acrylic polymer which uses chlorinated polyethylene as main elastomers and a coupling agent and a cross-linking agent as compatilizers and is prepared with the aid of polymerization and grafting of acrylic acid ester monomers. The AM mixture provided in the invention can effectively improve impact strength and tensile strength of a wood plastic product, provides the wood plastic product with certain processing performance, can effectively enhance compatibility among wood powder, calcium powder and PVC and dispersibility of the powders and enables weatherability of the wood plastic product to be well performed.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of AM mixture that is applied to wood plastic product and preparation thereof, application method.
Background technology
Wood plastic composite (Wood-Plastic Composites; WPC), be the one type of advanced composite material that is surging forward in recent years both at home and abroad, refer to utilize Vilaterm, Vestolen PP 7052 and SE etc.; Replace common resin adhesive; Be mixed into new wood materials with useless vegetable fibres such as surpassing wood powder more than the 35%-70%, rice husk, stalk, again through plastic processings such as extruding, mold pressing, injection moldings, sheet material of producing or section bar.Be mainly used in industries such as building materials, furniture, logistics packaging.With plastics with wooden powder mixes by a certain percentage after the sheet material of hot extrusion molding is referred to as to push wood-plastic composite panel.Wood is moulded the PVC matrix material as a kind of novel timber equivalent material; Can be widely used in fields such as building decoration and packing; Like corner line, wood shavings lath, curtain, door pocket, floor, hedge, baseboard, fine arts plate, window shutter, picture frame, photo frame, window frame, toy and common wealth furniture articles for use, interior door etc., most all available PVC Wood-plastic materials of indoor and outdoor decorative building material are made.It is worthy of note especially, come the processing and fabricating finishing material except bringing hidden fire-fighting danger, also go mouldy easily and damage by worms, bring potential safety hazard with log.And PVC wood is moulded the shortcoming that casts off log once and for all, has improved the deficiency of log, has kept the distinctive woodiness touch of log.Than timber, Wood-plastic material has waterproof, fire-proof function, thereby can be used for the decoration of kitchen, washroom etc.Simultaneously the PVC Wood-plastic material can be planted and color is produced the goods of different grades, different size, different colours according to different wood.Because production process adopts extrusion moulding, can realize automatic continuous production, length decides that arbitrarily this is that log institute can not reach.Wood plastic product has caused international extensive attention at present, is described as the environmental protection type material, will have vast potential for future development.
Mould blend of particles and make wooden moulding in the process of parts at preparation wood, various additives add in the wood plastic composite with independent powder, particle or liquid ingredient usually, so the preparation of these blends not only expensive but also complicacy.Therefore; Need obtain and to reduce cost; Mould the compositions of additives of the complicacy of blend but also can reduce the full preparation wood of preparation, also need obtain further to improve full preparation wood and mould the physics use properties of blend and the compositions of additives of processibility.
The impact modifying agent that is used for wood plastic composite is the particle that contains rubber, is dispersed in the whole thermoplastic resin.In general, these impact modifying agents comprise at least a rubber-like polymer particle that is surrounded by at least one hard polymer shell and use the emulsion polymerization method to prepare.The rubbery polymer part can make wood plastic composite absorb physical shock, prevents to begin cracking, and prevents to mould the cracking expansion in the parts at wood, can reduce fracture like this and increase shock strength.Separate because polymer beads often has viscosity and not can be used as dry powder, therefore often the hard polymer shell is added each rubber " nuclear " particulate outside, can prepare easy-to-use dry powder impact modifying agent like this.The hard polymer shell of impact modifying agent is selected compatible with wood plastic composite usually, and impact modifying agent is distributed in the Wood-plastic material when compounding easily like this.
Present domestic many enterprises are engaged in the production of wood plastic composite, but its weathering resistance problem becomes its widely used difficult problem of yoke.
Summary of the invention
The purpose of this invention is to provide a kind of AM mixture that is applied to wood plastic product and preparation thereof, application method; When can effectively improve wood plastic product impact strength, tensile strength; Again certain processing characteristics can be provided; Can effectively improve the consistency of wood powder, calcium powder and PVC and the dispersing property of powder again, its weather resistance is also well brought into play.
A kind of AM mixture that is applied to wood plastic product of the present invention, be a kind of be main elastomerics with chlorinatedpolyethylene, with coupling agent, linking agent as compatilizer; The acrylic polymer that is aided with the acrylic ester monomer graft polymerization, above raw material be according to the mass percent meter, chlorinatedpolyethylene 68%～77%; Acrylic ester monomer 22.5～31.5%; Linking agent and coupling agent 0.5%～3%, wherein, acrylic ester monomer is TEB 3K and Bing Xisuandingzhi; Both mass ratioes are 4: 1, and the mass ratio of linking agent and coupling agent is 2: 1.
Wherein, described linking agent is preferably DCP (Di Cumyl Peroxide 99).
Described coupling agent is preferably used silane coupling agent, can select KH-560 (γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane) for use.
The AM preparation process of mixture that is applied to wood plastic product of the present invention may further comprise the steps:
(1) the acrylic ester monomer emulsion is synthetic: in reaction kettle, add emulsifier sodium lauryl sulfate, initiator potassium persulfate, deionized water; Add acrylic ester monomer afterwards; The quality of emulsifying agent is 1～3% of an acrylic ester monomer quality; The quality of initiator is 1～2% of an acrylic ester monomer quality, and the quality of deionized water is 30～50% of an acrylic ester monomer quality, in 35～55 ℃ of following insulation reaction 2～3h; Be cooled to room temperature, obtain the acrylic ester monomer emulsion;
(2) preparation of AM mixture: in stainless steel autoclave, add deionized water, emulsifier sodium lauryl sulfate, initiator potassium persulfate and on the acrylic ester monomer emulsion that makes of step, add linking agent, coupling agent again, behind the vacuum pumping; Add chlorinatedpolyethylene and stir temperature reaction; The quality of deionized water is 20～30% of a chlorinatedpolyethylene quality, and the quality of emulsifying agent is 1～5% of a chlorinatedpolyethylene quality, and the quality of initiator is 1～3% of chlorinatedpolyethylene and an acrylic ester monomer quality; Keep temperature of reaction at 50 ± 0.5 ℃; Fast cooling when treating that the still internal pressure drops to 0.2MPa, discharging, filtration, breakdown of emulsion, vacuum-drying get final product.
The present invention when using in per 100 weight part SE this AM mixture addition be 2～4 weight parts.
The production process of wood plastic composite (comprising goods) is very big to its performance impact; Experiment shows: the ability of processing can cause that inadequately fiber dispersion is inhomogeneous with infiltration; Undue processing then can make fibre beakage and fracture, and the both can reduce the mechanical property of Wood-plastic material.In addition, prevent undue shear or high temperature produces problems such as thickener, if the single stage method continuous processing is the insufficient processing that will influence next step of devolatilization (main dehydration), and makes product that bubble arranged and the performance reduction.Main equipments twin screw extruder, twin screw extruder are incorgruous tapered twin screw extruder.
Incorgruous tapered dual-screw-stem machine is referred to as low speed, less energy-consumption type equipment, non-assembled screw rod.With general tapered dual-screw-stem machine ratio, be adapting to heat-sensitive resin processing needs, and requires the work range of screw design adaptation broad, few to the cutting action of xylon, resin after a little while still can homodisperse and with the complete fusion of material.Because wood powder, vegetable fibre proportion is little, loading level is big, the conventional model of charging zone volume ratio is wanted big, will be grown.If wood powder, vegetable fibre add-on are big, the molten resin rigidity is big, also requires the wheel casing of anti-the high back pressure, adopts compression and fusion is fast, metering zone is short screw rod, to guarantee that the xylon residence time short, prevents that it from rupturing and the coking thickener.
On wood plastic composite is made gordian technique, rapid progress has been arranged at present, has made and all reach advanced world standards on wood plastic composite manufacturing technology and the product performance, and move towards market-oriented rapidly, its main gordian technique have following some:
(1) raw material needs thorough drying
Wood powder is different from inorganic mineral, has usually up to the moisture content more than 10%, is prone to cause the fabricated product bubble when using without thorough drying, burns, thickener, influences products appearance, causes continuous shutdown cleaning equipment simultaneously, is difficult to continuous production.At first must carry out thorough drying to wood powder.
(2) to carry out surface treatment to wood powder
The wood powder surface is the polar hydrophilic material for the poly-hydroxy structure, and superpolymer generally is nonpolar lipophilicity substance, and the two is difficult to compatible, the affinity extreme difference, and with the two direct blend, goods become fragile, mechanical property is very poor as simply, can not be practical.As wood powder being carried out surface treatment through graft reaction; Can make on the xylon-the OH group on the grafting organic group; Make the wood powder surface become oleophilic substance, improved and the macromolecular interface adhesion of superpolymer, also make wood powder in matrix material, more be prone to be uniformly dispersed simultaneously; Form closely knit reticulated structure, thereby improve the stretching and the shock strength of matrix material.Generally all use silane coupling agent for wood powder/PVC.
(3) develop to the functional composite material direction.
Wood plastic composite has the double properties of timber and plastics concurrently, adds a certain amount of functional materials, can make it have highly anti-impact, performance such as ageing-resistant, fire-retardant.This patent adds the AM mixture, both can improve its high impact-resistance, makes it have good soffening again, has improved surface smoothness.
(4) little foaming technique
Usually the wood plastic composite one that does not foam is that density is all bigger; And the goods resin demand of equal volume is also many than foam material; The 2nd, rigidity and impact are poor, need to increase the section bar sectional area or change section bar cross-sectional shape and the affinity and the consistency that need to improve wood powder and PVC interface.The 3rd, production efficiency is low, needs to increase fixed capital.So the fine foaming wood plastic composite materials as the development of plastic working regeneration product rapidly.
A kind of excellent wood plastic product prescription of the AM of use mixture is provided in this patent,, fills a prescription as follows according to the parts by weight meter:
Wherein, ACR processing aid LS-401 and foaming control agent LS-530 all purchase the Rui Feng macromolecular material limited-liability company in Shandong.
The invention has the advantages that: chlorinatedpolyethylene is combined acrylic ester monomer, and need not encasement.Chlorinatedpolyethylene is a kind of saturated rubber, has excellent weathering resistance, ageing-resistant performance, oil-proofness and flame retardant resistance, and good shock resistance and tensile strength, and price economy material benefit have good consistency with other macromolecular material.Compared with mould independent impact modifying agent and the processing aid that uses equal quantities in the prescription at wood, AM mixture of the present invention also provides high impact strength and good processing characteristics.Strengthening shock strength is because the chlorinatedpolyethylene particulate is provided, and excellent powder property and processing aid function provide by these high rubber chlorinatedpolyethylene particles and acrylic ester monomer are carried out the grafting coating.AM mixture of the present invention makes the wood and plastic composite material formula have following advantage: additive is moulded through using less hammer butt in (1), and impact modification rubber reduces cost cheaply; (2) weathering resistance and the tensile strength of goods have been improved.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
Embodiment 1:
(1) preparation of AM mixture:
Synthesizing of acrylic ester monomer emulsion: in reaction kettle, add 6g sodium lauryl sulphate, 3g Potassium Persulphate, 100g deionized water, stir and logical nitrogen, add 225.6g TEB 3K, 56.4g Bing Xisuandingzhi after 20 minutes, use Na
2SO
4It is 8 that solution is regulated the emulsion pH value, and in 50 ℃ of following insulation reaction 2h, cooling obtains the acrylic ester monomer emulsion;
The preparation of AM mixture: in stainless steel autoclave, add 200 deionized waters, 12g sodium lauryl sulphate, 12g Potassium Persulphate and on the acrylic ester monomer emulsion 818g that makes of step; Contain acrylic ester monomer 282g, the pH value of regulating mixed reaction solution with 5%～10%NaOH solution adds 18g crosslink agent DCP and silane coupling agent KH-560 again in 9～11 scopes; Fill nitrogen and vacuumize deoxygenation; After 3 times, add the 900g chlorinatedpolyethylene and stir temperature reaction repeatedly, keep temperature of reaction at 50 ± 0.5 ℃; Fast cooling when treating that the still internal pressure drops to 0.2MPa; Discharging, filtration, breakdown of emulsion, vacuum-drying get the compound resin powder, and the gained material is that to have rubbery kernel be the nuclear-shell AM compound particles of 130 nanometers with outer hard median size mutually.
(2) Wood-plastic foam preparation of plates
By following prescription, with incorgruous tapered twin screw extruder and related die extrusion board.
Machining control technology:
Material residence time in extruder barrel and mouthful mould is controlled at 8～10min and is advisable, and the density of end article is suitable like this.Through cooling, typing, traction, cutting, it is to be tested to get smooth section of smooth surface.
Embodiment 2～3:
Synthetic AM mixture conditions and ratio change, and produce the Wood-plastic foam plate prescription and change, and concrete prescription is seen table 1;
Comparative Examples 1～2:
Select Japanese clock deep pool FM-50 impact modifier for use, LS-401 uses with processing aid, and concrete prescription is seen table 1.
Table 1:
The application performance data contrast of embodiment 1～3 and Comparative Examples 1,2:
According to experimental result, can produce according to the present invention and to extrude wood plastic product, can make have excellent weather resistance, abscess evenly, any surface finish, dimensional stabilizing, the wood plastic product that intensity is high.
Claims (5)
1. AM mixture that is applied to wood plastic product, it is characterized in that be a kind of be main elastomerics with chlorinatedpolyethylene, with coupling agent, linking agent as compatilizer; The acrylic polymer that is aided with the acrylic ester monomer graft polymerization, above raw material be according to the mass percent meter, chlorinatedpolyethylene 68%～77%; Acrylic ester monomer 22.5～31.5%; Linking agent and coupling agent 0.5%～3%, wherein, acrylic ester monomer is TEB 3K and Bing Xisuandingzhi; Both mass ratioes are 4: 1, and the mass ratio of linking agent and coupling agent is 2: 1.
2. the AM mixture that is applied to wood plastic product according to claim 1 is characterized in that linking agent is DCP.
3. the AM mixture that is applied to wood plastic product according to claim 1 is characterized in that coupling agent selects silane coupling agent for use, preferably uses KH-560.
4. described AM preparation process of mixture that is applied to wood plastic product of claim 1 is characterized in that may further comprise the steps:
(1) the acrylic ester monomer emulsion is synthetic: in reaction kettle, add emulsifier sodium lauryl sulfate, initiator potassium persulfate, deionized water; Add acrylic ester monomer afterwards; The quality of emulsifying agent is 1～3% of an acrylic ester monomer quality; The quality of initiator is 1～2% of an acrylic ester monomer quality, and the quality of deionized water is 30～50% of an acrylic ester monomer quality, in 35～55 ℃ of following insulation reaction 2～3h; Be cooled to room temperature, obtain the acrylic ester monomer emulsion;
(2) preparation of AM mixture: in stainless steel autoclave, add deionized water, emulsifier sodium lauryl sulfate, initiator potassium persulfate and on the acrylic ester monomer emulsion that makes of step, add linking agent, coupling agent again, behind the vacuum pumping; Add chlorinatedpolyethylene and stir temperature reaction; The quality of deionized water is 20～30% of a chlorinatedpolyethylene quality, and the quality of emulsifying agent is 1～5% of a chlorinatedpolyethylene quality, and the quality of initiator is 1～3% of chlorinatedpolyethylene and an acrylic ester monomer quality; Keep temperature of reaction at 50 ± 0.5 ℃; Fast cooling when treating that the still internal pressure drops to 0.2MPa, discharging, filtration, breakdown of emulsion, vacuum-drying get final product.
5. the described application method that is applied to the AM mixture of wood plastic product of claim 1 is characterized in that this AM mixture addition is 2～4 weight parts in SE 100 weight parts.
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| CN103255995A (en) * | 2012-07-12 | 2013-08-21 | 阮班雨 | Manufacturing process of waterproof blind curtains |
| CN106366223A (en) * | 2016-08-30 | 2017-02-01 | 山东东临新材料股份有限公司 | Method for preparing CPVC impact modifier |
| CN110016105A (en) * | 2019-04-25 | 2019-07-16 | 青岛中塑高新材料有限公司 | A kind of PVC wood plastic foaming product lubrication forming agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103255995A (en) * | 2012-07-12 | 2013-08-21 | 阮班雨 | Manufacturing process of waterproof blind curtains |
| CN103255995B (en) * | 2012-07-12 | 2016-01-06 | 阮班雨 | The manufacturing process of water-proof shutters curtain |
| CN106366223A (en) * | 2016-08-30 | 2017-02-01 | 山东东临新材料股份有限公司 | Method for preparing CPVC impact modifier |
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| CN110016105A (en) * | 2019-04-25 | 2019-07-16 | 青岛中塑高新材料有限公司 | A kind of PVC wood plastic foaming product lubrication forming agent and preparation method thereof |
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| CN102492239B (en) | 2014-01-01 |
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