CN102492239B - AM mixture used for wood plastic products, and application methods thereof - Google Patents

AM mixture used for wood plastic products, and application methods thereof Download PDF

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CN102492239B
CN102492239B CN201110388812.4A CN201110388812A CN102492239B CN 102492239 B CN102492239 B CN 102492239B CN 201110388812 A CN201110388812 A CN 201110388812A CN 102492239 B CN102492239 B CN 102492239B
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ester monomer
acrylic ester
mixture
wood plastic
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CN102492239A (en
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朱西堂
刘春信
葛峰
咸春蕾
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SHANDONG RUIFENG POLYMER MATERIAL CO Ltd
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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

Be applied to the AM mixture of wood plastic product and preparation thereof, application method
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), it is the class advanced composite material in recent years be surging forward both at home and abroad, refer to utilize polyethylene, polypropylene and polyvinyl chloride etc., replace common resin adhesive, be mixed into new wood materials with useless vegetable fibres such as surpassing wood powder more than 35%-70%, rice husk, stalk, then through the plastic processings such as extruding, mold pressing, injection molding, the sheet material of producing or section bar.Be mainly used in the industries such as building materials, furniture, logistics packaging.Plastics and wooden powder are mixed to the sheet material by hot extrusion molding by a certain percentage, be referred to as to push wood-plastic composite panel.Wood is moulded the PVC matrix material as a kind of novel wood substitute material, can be widely used in the fields such as building decoration and packing, as 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 indoor and outdoor decorative building materials all can be manufactured with the PVC Wood-plastic material.It is worthy of note especially, with log, come the processing and fabricating finishing material except bringing hidden fire-fighting danger, also easily go mouldy and damage by worms, bring potential safety hazard.And PVC wood is moulded the shortcoming that casts off log once and for all, improved the deficiency of log, retained 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 arbitrarily, this is that log can not reach.Wood plastic product has now caused international extensive attention, is described as the environmental protection type material, will have vast potential for future development.
Mould blend of particles and manufacture during wood moulds the process of parts at preparation wood, various additives add in wood plastic composite with independent powder, particle or liquid ingredient usually, so the preparation of these blends not only price but also complexity.Therefore, need to obtain reducing costs, mould the compositions of additives of the complicacy of blend but also can reduce the full preparation wood of preparation, also need to obtain further improving full preparation wood and mould the physics use properties of blend and the compositions of additives of processibility.
Impact modifying agent for wood plastic composite is the particle containing rubber, is dispersed in whole thermoplastic resin.In general, these impact modifying agents comprise at least one rubber-like polymer particle surrounded by least one hard polymer shell and prepare by the emulsion polymerization method.The rubbery polymer part can make wood plastic composite absorb physical shock, prevents from starting cracking, and prevents from moulding the cracking expansion in parts at wood, can reduce and ruptures and increase shock strength like this.Separate because polymer beads often has viscosity and not can be used as dry powder, therefore often the hard polymer shell is added to the outside of each rubber " core " particle, can prepare so easy-to-use dry powder impact modifying agent.The hard polymer shell of impact modifying agent is selected compatible with wood plastic composite usually, during impact modifying agent easily is distributed to Wood-plastic material when compounding like this.
Current 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, can provide certain processing characteristics again, 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, a kind ofly to take chlorinatedpolyethylene as main elastomerics, using coupling agent, linking agent as compatilizer, the acrylic polymer that is aided with the acrylic ester monomer graft polymerization, above raw material is 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 methyl methacrylate and butyl acrylate, and 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 (dicumyl peroxide).
Described coupling agent is preferably used silane coupling agent, can select KH-560 (γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane).
The preparation method who is applied to the AM mixture of wood plastic product of the present invention comprises the following steps:
(1) the acrylic ester monomer emulsion is synthetic: add emulsifier sodium lauryl sulfate, initiator potassium persulfate, deionized water in reactor, add afterwards acrylic ester monomer, the quality of emulsifying agent is 1~3% of acrylic ester monomer quality, the quality of initiator is 1~2% of acrylic ester monomer quality, the quality of deionized water is 30~50% of acrylic ester monomer quality, in 35~55 ℃ of lower insulation reaction 2~3h, be cooled to room temperature, obtain the acrylic ester monomer emulsion;
(2) preparation of AM mixture: add deionized water in stainless steel autoclave, emulsifier sodium lauryl sulfate, the acrylic ester monomer emulsion that initiator potassium persulfate and upper step make, add again linking agent, coupling agent, after vacuum pumping, add chlorinatedpolyethylene to stir temperature reaction, the quality of deionized water is 20~30% of chlorinatedpolyethylene quality, the quality of emulsifying agent is 1~5% of chlorinatedpolyethylene quality, the quality of initiator is 1~3% of chlorinatedpolyethylene and acrylic ester monomer quality, maintain temperature of reaction at 50 ± 0.5 ℃, fast cooling when the still internal pressure drops to 0.2MPa, discharging, filter, breakdown of emulsion, vacuum-drying gets final product.
The present invention's this AM mixture addition in when application every 100 weight part polyvinyl chloride is 2~4 weight parts.
The production process of wood plastic composite (comprising goods) is very large to its performance impact, experiment shows: the ability of processing can cause not fiber dispersion and infiltrate inhomogeneous, undue processing can make fibre beakage and fracture, both can reduce the mechanical property of Wood-plastic material.In addition, prevent that too shearing or high temperature from producing the problems such as thickener, if the insufficient processing that will affect next step of single stage method continuous processing devolatilization (main dehydration), and make product that bubble be arranged and the performance reduction.Main processing units twin screw extruder, twin screw extruder is 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, for adapting to heat-sensitive resin processing needs, require screw design to adapt to wider work range, few to the cutting action of xylon, resin while lacking, still can be uniformly dispersed and with the complete melting of material.Due to wood powder, vegetable fibre proportion is little, loading level is large, the conventional model of charging zone volume ratio is wanted large, will be grown.If wood powder, vegetable fibre add-on are large, the molten resin rigidity is large, also requires the wheel casing of anti-the high back pressure, adopts compression and melting is fast, metering zone is short screw rod, short to guarantee the xylon residence time, prevents that it from rupturing and the coking thickener.
On wood plastic composite is manufactured gordian technique, rapid progress has been arranged at present, has made on wood plastic composite manufacturing technology and product performance and all reach advanced world standards, and move towards rapidly market-oriented, its main gordian technique have following some:
(1) raw material needs fully dry
Wood powder is different from inorganic mineral, usually have up to the moisture content more than 10%, without fully dry and easily cause the fabricated product bubble while using, burn, thickener, affect products appearance, cause continuous stop cleaning equipment simultaneously, be difficult to continuous production.At first must carry out abundant 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 is generally nonpolar lipophilicity substance, and the two is difficult to compatible, the affinity extreme difference, and as simply, by the two direct blend, goods become fragile, mechanical property is very poor, can not be practical.As by graft reaction, wood powder carried out to surface treatment, grafting organic group on can make on xylon-OH group, make the wood powder surface become oleophilic substance, improved and the macromolecular interface adhesion of superpolymer, also make wood powder more easily be uniformly dispersed in matrix material simultaneously, form closely knit reticulated structure, thereby improve stretching and the shock strength of matrix material.Generally all use silane coupling agent for wood powder/PVC.
(3) to the functional composite material future development.
Wood plastic composite has the double properties of timber and plastics concurrently, adds a certain amount of functional materials, can make it have high impact-resistant, the performance such as ageing-resistant, fire-retardant.This patent adds the AM mixture, both can improve its high impact-resistance, makes again it have good soffening, has improved surface smoothness.
(4) micro-foaming technique
Usually the wood plastic composite one do not foamed is that density is all larger, 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 the section bar cross-sectional shape and need to improve affinity and the consistency at 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 formula of the AM of use mixture is provided in this patent, according to the parts by weight meter, fills a prescription as follows:
Figure BDA0000114256290000041
Wherein, ACR processing aid LS-401 and foaming control agent LS-530 all are purchased from Shandong Rui Feng macromolecular material limited-liability company.
The invention has the advantages that: by chlorinatedpolyethylene in conjunction with acrylic ester monomer, and without 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 formula 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 being carried out to the grafting coating.AM mixture of the present invention makes the wood and plastic composite material formula have following advantage: (1) is by using less hammer butt to mould additive, and impact modification rubber reduces costs cheaply; (2) weathering resistance and the tensile strength of goods have been improved.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1:
(1) preparation of AM mixture:
Synthesizing of acrylic ester monomer emulsion: add 6g sodium lauryl sulphate, 3g Potassium Persulphate, 100g deionized water in reactor, stir and logical nitrogen, add 225.6g methyl methacrylate, 56.4g butyl acrylate after 20 minutes, use Na 2sO 4it is 8 that solution is regulated the emulsion pH value, and in 50 ℃ of lower insulation reaction 2h, cooling, obtain the acrylic ester monomer emulsion;
The preparation of AM mixture: add 200 deionized waters in stainless steel autoclave, the 12g sodium lauryl sulphate, the acrylic ester monomer emulsion 818g that 12g Potassium Persulphate and upper step make, contain acrylic ester monomer 282g, regulate the pH value of mixed reaction solution in 9~11 scopes with 5%~10%NaOH solution, add again 18g crosslink agent DCP and silane coupling agent KH-560, fill nitrogen and vacuumize deoxygenation, repeatedly after 3 times, add the 900g chlorinatedpolyethylene to stir temperature reaction, maintain temperature of reaction at 50 ± 0.5 ℃, fast cooling when the still internal pressure drops to 0.2MPa, discharging, filter, breakdown of emulsion, vacuum-drying obtains the compound resin powder, the gained material is to have the core that the median size of rubbery kernel and outer hard phase is 130 nanometers-shell AM compound particles.
(2) Wood-plastic foam preparation of plates
According to the following formulation, with incorgruous tapered twin screw extruder and related die extrusion board.
Figure BDA0000114256290000051
Machining control technique:
Figure BDA0000114256290000052
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, get smooth section of smooth surface to be tested.
Embodiment 2~3:
Synthetic AM mixture conditions and ratio change, and produce the Wood-plastic foam plate prescription and change, and specifically fill a prescription in Table 1;
Comparative Examples 1~2:
Select Japanese clock deep pool FM-50 impact modifier, with processing aid, LS-401 is mixed, specifically fills a prescription in Table 1.
Table 1:
Figure BDA0000114256290000061
The application performance Data Comparison of embodiment 1~3 and Comparative Examples 1,2:
According to experimental result, can produce and extrude wood plastic product according to the present invention, can make have excellent weather resistance, abscess evenly, any surface finish, dimensional stabilizing, the wood plastic product that intensity is high.

Claims (5)

1. an AM mixture that is applied to wood plastic product, it is characterized in that a kind ofly take chlorinatedpolyethylene as main elastomerics, using coupling agent, linking agent as compatilizer, be aided with the acrylic ester monomer graft polymerization and obtain acrylic polymer, above raw material is 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 methyl methacrylate and butyl acrylate, and 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.
4. a preparation method who is applied to the AM mixture of wood plastic product claimed in claim 1 is characterized in that comprising the following steps:
(1) the acrylic ester monomer emulsion is synthetic: add emulsifier sodium lauryl sulfate, initiator potassium persulfate, deionized water in reactor, add afterwards acrylic ester monomer, the quality of emulsifying agent is 1~3% of acrylic ester monomer quality, the quality of initiator is 1~2% of acrylic ester monomer quality, the quality of deionized water is 30~50% of acrylic ester monomer quality, in 35~55 ℃ of lower insulation reaction 2~3h, be cooled to room temperature, obtain the acrylic ester monomer emulsion;
(2) preparation of AM mixture: add deionized water in stainless steel autoclave, emulsifier sodium lauryl sulfate, the acrylic ester monomer emulsion that initiator potassium persulfate and upper step make, add again linking agent, coupling agent, after vacuum pumping, add chlorinatedpolyethylene to stir temperature reaction, the quality of deionized water is 20~30% of chlorinatedpolyethylene quality, the quality of emulsifying agent is 1~5% of chlorinatedpolyethylene quality, the quality of initiator is 1~3% of chlorinatedpolyethylene and acrylic ester monomer quality, maintain temperature of reaction at 50 ± 0.5 ℃, fast cooling when the still internal pressure drops to 0.2MPa, discharging, filter, breakdown of emulsion, vacuum-drying gets final product.
5. an application method that is applied to the AM mixture of wood plastic product claimed in claim 1, is characterized in that in polyvinyl chloride 100 weight parts, this AM mixture addition is 2~4 weight parts.
CN201110388812.4A 2011-11-30 2011-11-30 AM mixture used for wood plastic products, and application methods thereof Active CN102492239B (en)

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CN103255995B (en) * 2012-07-12 2016-01-06 阮班雨 The manufacturing process of water-proof shutters curtain
CN106366223B (en) * 2016-08-30 2019-09-20 山东东临新材料股份有限公司 The preparation method of 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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CN1498917A (en) * 2002-11-08 2004-05-26 华昌工贸有限公司 Polypropylene(PP)-wood plate
CN1513918A (en) * 2002-12-31 2004-07-21 中国石油化工股份有限公司 Wood plastic composite material and its preparation method and application
CN1827680A (en) * 2006-03-28 2006-09-06 广东工业大学 Formulation for preparing PVC-base wood-plastic composite materials
CN101328240A (en) * 2007-06-18 2008-12-24 沂源瑞丰高分子材料有限公司 Weather resistant, impact resistant and economical PVC promoter
CN101691059A (en) * 2009-09-25 2010-04-07 丹阳市圣象地板配件有限公司 Production technology of wood plastic skirting board
CN101864130A (en) * 2010-07-26 2010-10-20 南京皇家聚锋建筑材料有限公司 PVC plastic-wood material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1498917A (en) * 2002-11-08 2004-05-26 华昌工贸有限公司 Polypropylene(PP)-wood plate
CN1513918A (en) * 2002-12-31 2004-07-21 中国石油化工股份有限公司 Wood plastic composite material and its preparation method and application
CN1827680A (en) * 2006-03-28 2006-09-06 广东工业大学 Formulation for preparing PVC-base wood-plastic composite materials
CN101328240A (en) * 2007-06-18 2008-12-24 沂源瑞丰高分子材料有限公司 Weather resistant, impact resistant and economical PVC promoter
CN101691059A (en) * 2009-09-25 2010-04-07 丹阳市圣象地板配件有限公司 Production technology of wood plastic skirting board
CN101864130A (en) * 2010-07-26 2010-10-20 南京皇家聚锋建筑材料有限公司 PVC plastic-wood material

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