CN102838816A - New macromolecule fiber composite material - Google Patents
New macromolecule fiber composite material Download PDFInfo
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- CN102838816A CN102838816A CN2012103340025A CN201210334002A CN102838816A CN 102838816 A CN102838816 A CN 102838816A CN 2012103340025 A CN2012103340025 A CN 2012103340025A CN 201210334002 A CN201210334002 A CN 201210334002A CN 102838816 A CN102838816 A CN 102838816A
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Abstract
The invention discloses a new macromolecule fiber composite material which is prepared by the following components in parts by weight, 40-100 parts of plant fiberfill, 60-100 parts of plastic base material, 3.5-5 parts of heat stabilizer, 1-2 parts of plasticizer, 1.6-2 parts of lubricating agent, 4-8 parts of modifying agent, 1-3 parts of compatilizer, 2-3 parts of coupling reagent, 1-5 parts of super dispersing agent, 1-4 parts of positive ion surface active agent, 1-1.8 parts of foaming agent, 1-5 parts of blowing promoter, 0.3-1.2 parts of antioxygen, 1-10 parts of cross-linking agent, 1-20 parts of nucleating agent, 0.8-1 part of viscosity reducer, 0.8-1 part of tackifier and 3.2-13.4 parts of other auxiliaries. The new composite material can not easily cause wet swelling and air shrinkage, and is low in expansibility and water absorbability, so that the prepared product has good stability.
Description
Technical field
The present invention relates to macromolecular material and goods field, be specifically related to a kind of macromolecular fibre composite material with the biomass source.
Background technology
The macromolecular fibre composite material is vegetable fibre (comprising wood chip, sisal hemp powder, bagasse, bamboo bits, waste of flax, shell etc.) and plastics to be carried out blend extrude the one type of matrix material that obtains, and is widely used in industry fields such as covil construction decoration, car and boat, national defence.This type material has processibility preferably, and having simultaneously has characteristics such as anticorrosive, attractive in appearance, generous, but that its weak point is a mechanical property is not good enough, but can be through vegetable fibre and plastics being carried out surface-treated, adding different auxiliary agents and improve.Publication number is the patent of invention of CN101921491A, discloses a kind of wood plastic composite, by weight meter; Comprise 100 parts of wood powders, 20～80 parts of plastic waste, 5～50 parts of waste rubbers; High molten 10～60 parts of thermoplastic resins, 1～12 part in tensio-active agent, 2～8 parts of the lubricants of referring to; 0.1～4 part of linking agent, 0.1～4 part in oxidation inhibitor, 0.05～1.5 part of processing aid; Wherein, said wood powder order number is at 10 to 325 orders, and the high molten melt flow rate that refers to thermoplastic resin is more than 20g/10min, and linking agent is a superoxide.This invention through add high molten refer to thermoplastic resin, tensio-active agent improve the dispersiveness of wood powder in the mixture, flowability and with the consistency of plastic cement, through adding the mechanical property (like tensile strength, bending strength, shock strength etc.) of waste rubber with the raising material.But rubber all is to derive from oil basically, belongs to inflammable substance, if on building and ornament materials, use, has potential safety hazard.
Summary of the invention
The technical problem that the present invention will solve provides a kind of macromolecular fibre composite material, and this material has mechanical property and lower rate of expansion preferably.
Macromolecular fibre composite material of the present invention, by weight, it is processed by following component:
40～100 parts of vegetable fibre fillers; 60～100 parts of plastic basis materials;
3.5～5 parts of thermo-stabilizers; 1～2 part in softening agent;
1.6～2 parts of lubricants; 4～8 parts of properties-correcting agent;
1～3 part of compatilizer; 2～3 parts of coupling agents;
1～5 part of hyper-dispersant; 1～4 part of cats product;
1～1.8 part of whipping agent; 1～5 part of frothing aid;
0.3～1.2 part in oxidation inhibitor; 1～10 part of linking agent;
1～20 part of nucleator; 0.8～1 part of viscosity-depression agent;
0.8～1 part of tackifier; 3.2～13.4 parts of other auxiliary agents;
Wherein,
Described thermo-stabilizer is organotin stabilizer, calcium zinc stabilizer or lead salt one package stabilizer;
Described properties-correcting agent is ACR-401, Injecatable EVA Copolymer or chlorinatedpolyethylene;
Described cats product is a quaternary ammonium salt cationic surfactant;
Described whipping agent is the combination of sodium hydrogencarbonate and Cellmic C 121 or the fine any proportioning of azo two isobutyls;
Described nucleator is a kind of or two or more combination arbitrarily that is selected from calcium carbonate crystal whisker, nano active light calcium carbonate, talcum powder, titanium oxide and the calcium stearate;
Described other auxiliary agent by weight, it consists of 0.5～1.2 part of 0.5～3 part in sodium hydroxide, 1～5 part in urea, 1～3 part of Paraformaldehyde 96,0.2～1.2 part in formic acid and trimeric cyanamide.
The weight part of each component is preferably in the above-mentioned macromolecular fibre composite material:
50～100 parts of vegetable fibre fillers; 60～80 parts of plastic basis materials;
4～5 parts of thermo-stabilizers; 1～2 part in softening agent;
1.8～2 parts of lubricants; 5～7.5 parts of properties-correcting agent;
1.5～3 parts of compatilizers; 2～3 parts of coupling agents;
2～4 parts of hyper-dispersants; 1～2 part of cats product;
1.2～1.6 parts of whipping agents; 2～5 parts of frothing aids;
0.5～1 part in oxidation inhibitor; 1～5 part of linking agent;
5～13 parts of nucleators; 0.8～0.9 part of viscosity-depression agent;
0.8～0.9 part of tackifier; 4.7～6.7 parts of other auxiliary agents.
In the technique scheme:
Described vegetable fibre filler can be the fine particle that obtains after wood (bamboo) this material is pulverized like sawdust, wood shavings, wood chip, coconut husk, bamboo bits or bamboo suede etc.; It also can be the fine particle that obtains after draft material such as sisal hemp tankage, wood chip, shell, waste of flax, Pericarppium arachidis hypogaeae, chestnut shell, bagasse etc. are pulverized; Can also be any two or more combination in the above-mentioned selection, the proportioning between them can be any proportioning at this moment.The granularity of said vegetable fibre filler is controlled at 80～200 orders usually.
Described plastic basis material can be a thermoplastics, like SE (PVC), Vilaterm (PE), Vestolen PP 7052 (PP), nylon (PA), PS (PS) or acrylonitrile-butadiene-styrene copolymer (ABS) etc.; Also can be thermosetting resin, like amine resin, resol or epoxy resin etc.; Can also be any two or more combination in the above-mentioned selection, the proportioning between them can be any proportioning at this moment.Described plastic basis material can be virgin material or reclaimed materials, and its granularity is controlled at 20～100 orders usually.
Described softening agent is one or more the combination that is selected from DOP, Witcizer 300 and the epoxy soybean oil; When softening agent was above-mentioned arbitrarily two or more combination, the proportioning between them can be any proportioning.
Described lubricant is to be selected from a kind of or two or more combination arbitrarily in cured of Triple Pressed Stearic Acid, lead stearate, barium stearate, Zinic stearas, paraffin, polyethylene wax and oxidic polyethylene; When lubricant was above-mentioned arbitrarily two or more combination, the proportioning between them can be any proportioning.
ACR-401 in the said properties-correcting agent is an acrylic acid lipid high-molecular copolymer, specifically can adopt Zibo Huaxing Additives Co., Ltd., Zibo seaization chemical industry ltd, Shangyu city near a river company such as chemical industry ltd produce.
Described compatilizer is Vilaterm lactone, maleic anhydride, vinylformic acid or gathers the methylpropanoic acid formicester.
Described coupling agent is a kind of or two or more combination arbitrarily that is selected from silane coupling agent, titanate coupling agent and the aluminate coupling agent.Wherein silane coupling agent can be r-aminopropyl three ethoxy silane (KH550), r-Racemic glycidol oxygen propyl trimethoxy silicane (KH560), trifluoro propyl Trimethoxy silane (TF3) or 17 fluorine decyl Trimethoxy silanes (TF17); Titanate coupling agent can be titanate coupling agent NDZ-102, titanate coupling agent NDZ-201, titanate coupling agent NDZ-210, titanate coupling agent NDZ-331 or titanate coupling agent NDZ-401; Aluminate coupling agent can be aluminate coupling agent DL-441-A, aluminate coupling agent DL-481 or aluminate coupling agent DL-427.When the above-mentioned arbitrarily two or more combination of being chosen as of coupling agent, the proportioning between them can be any proportioning.
Described hyper-dispersant has another name called super dispersion agent, specifically can be that the trade mark is NBZ-3, DA-50, WH-1 or PD-5 hyper-dispersant (national ultrafine powder ERC, Huaming Superfine New Material Co., Ltd., Shanghai and the chemical physics Institute of technology of East China University of Science develop jointly); It also can be CH series hyper-dispersant (ShangHai SanZheng polymer Materials Co., Ltd); The preferred hyperbranched dispersion agent (Guilin University of Technology's development is also produced) that uses.
Described cats product is a quaternary ammonium salt cationic surfactant, specifically can be alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt or alkyl dimethyl benzyl ammonium salt etc.Wherein said alkyl dimethyl benzyl ammonium salt typically refers to alkyldimethylbenzyl ammonium lauryl sulfate or lauryl sulfate didecyldimethyl ammonium.
Described frothing aid specifically can be to be foaming control agent ZB530 (Shandong China star additives for plastics is produced).
Described oxidation inhibitor can be DBPC 2,6 ditertiary butyl p cresol or four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester.
Described linking agent can be Lucidol, Di Cumyl Peroxide 99 or peroxidized t-butyl perbenzoate.
The adding of nucleator also can further improve the mechanical property of product; When nucleator be chosen as any two or more combination in calcium carbonate crystal whisker, nano active light calcium carbonate, talcum powder, titanium oxide and the calcium stearate time, the proportioning between them can be any proportioning.
The polymerization degree of the Paraformaldehyde 96 in the said processing aid is less than 8; Preferred degree of polymerization is 2～8 Paraformaldehyde 96; Specifically can be low polymerization degree Paraformaldehyde 96 (formaldehyde content is 77%～93% methylene glycol polycondensate), be solid powdery (Shouguang City, Shandong rising sun east chemical industry ltd produces).
Described viscosity-depression agent is viscosity-depression agent LJ-950.
Described tackifier are polystyrene resin, mono-laurate polyoxyethylene compound or ethylene oxide-propylene oxide block copolymer.
The preparation method of macromolecular fibre composite material according to the invention is:
The vegetable fibre filler is placed high-speed mixer, add other auxiliary agent and mix stirring 3～6min (expect that temperature reaches 100 ℃～120 ℃ this moment), open the hopper cover on the high-speed mixer; Let contained moisture content distributes in the vegetable fibre filler, when treating that temperature of charge is reduced to 45～55 ℃, add hyper-dispersant and cats product again; Mix and stir 1～2min; When treating that temperature of charge is reduced to 55～65 ℃, add plastic basis material and thermo-stabilizer, mix and stir 1～2min; When treating that temperature of charge is reduced to 65～75 ℃; Add lubricant, properties-correcting agent, compatilizer, coupling agent, oxidation inhibitor, linking agent, viscosity-depression agent and tackifier and mix stirring 2～4min; Treat to add when temperature of charge is reduced to 75～85 ℃ softening agent and mix stirring 2～3min; Add whipping agent when treating that temperature of charge is reduced to 85～95 ℃ and mix with frothing aid and stir 2～3min, adding nucleator when treating that temperature of charge is reduced to 95～105 ℃ mixes to and stops mixed at high speed when temperature of charge reaches 120 ℃; Material is discharged, and single screw rod sent into by gained premix material or dual-screw pelletizer carries out granulation (processing temperature is 140～170 ℃); At last pellet is sent into single screw rod or twin screw extruder (processing temperature is 150～175 ℃) is extruded various macromolecular fibre composite material goods base materials, through water-cooled shaping, traction, cutting, blanking, obtain finished product again.
Macromolecular fibre composite material according to the invention selects for use other auxiliary agent of special proportioning that the vegetable fibre filler is carried out modification; Plug with molten metal effect through the polar group generation anchor on the vegetable fibre filling surface after hyper-dispersant, cats product and the modification again; To reduce the surface polarity of vegetable fibre filler; On the one hand, help vegetable fibre filler and plastic basis material blend, solve the compatibility problem between both interfaces; On the other hand; Can improve the affinity between vegetable fibre filler and the plastic basis material; Form closely knit reticulated structure, make the dispersion of vegetable fibre filler in matrix material more even, mobile better; Thereby can transmit the stress between filler and the resin well, and then improve the mechanical property of product greatly.Simultaneously; Because the adding of hyper-dispersant; Polarity hydroxyl in the vegetable fibre filler after the modification is replaced by the substituting group in the relevant auxiliary agent or coated by plastic basis material; Thereby make prepared matrix material be difficult for bulking and drying shrinkage take place, rate of expansion and water-absorbent rate are low, thereby resulting product has stability preferably; And the adding of cats product also make the surface of extruded product more smooth, more attractive in appearance, and have better erosion resistance.
Embodiment
With specific embodiment the present invention is described further below, but the present invention is not limited to these embodiment.
Below each embodiment all adopt following method to process:
The vegetable fibre filler is placed high-speed mixer, add other auxiliary agent and mix stirring 5min, open the hopper cover on the high-speed mixer then; Let contained moisture content distributes in the vegetable fibre filler, when treating that temperature of charge is reduced to 50 ℃, add hyper-dispersant and cats product; Mix and stir 2min; When treating that temperature of charge is reduced to 60 ℃, add plastic basis material and thermo-stabilizer, mix and stir 2min; When treating that temperature of charge is reduced to 70 ℃; Add lubricant, properties-correcting agent, compatilizer, coupling agent, oxidation inhibitor, linking agent, viscosity-depression agent and tackifier and mix stirring 3min; Treat to add when temperature of charge is reduced to 80 ℃ softening agent and mix stirring 3min; Add whipping agent when treating that temperature of charge is reduced to 90 ℃ and mix with frothing aid and stir 3min, adding nucleator when treating that temperature of charge is reduced to 100 ℃ mixes to and stops mixed at high speed when temperature of charge reaches 120 ℃; Material is discharged, and single screw rod sent into by gained premix material or dual-screw pelletizer carries out granulation (processing temperature is 140～170 ℃); At last pellet is sent into single screw rod or twin screw extruder (processing temperature is 150～175 ℃) is extruded various macromolecular fibre composite material goods base materials, through water-cooled shaping, traction, cutting, blanking, obtain finished product again.
Embodiment 1
Prescription according to embodiment 1 in the below table 1 takes by weighing each component, processes sheet material as stated above.
Embodiment 2
Prescription according to embodiment 2 in the below table 1 takes by weighing each component, processes sheet material as stated above.
Embodiment 3
Prescription according to embodiment 3 in the below table 1 takes by weighing each component, processes sheet material as stated above.
Embodiment 4
Prescription according to embodiment 4 in the below table 1 takes by weighing each component, processes sheet material as stated above.
Embodiment 5
Prescription according to embodiment 5 in the below table 1 takes by weighing each component, processes sheet material as stated above.
Embodiment 6
Prescription according to embodiment 6 in the below table 1 takes by weighing each component, processes sheet material as stated above.
Table 1:
The sheet material that makes according to embodiment 1～6 is carried out melting index, flexural strength, tensile strength, resistance to impact shock, water-intake rate test, the result is shown in below table 2:
Table 2:
Claims (9)
1. macromolecular fibre composite material, it is characterized in that: by weight, it is processed by following component:
40～100 parts of vegetable fibre fillers; 60～100 parts of plastic basis materials;
3.5～5 parts of thermo-stabilizers; 1～2 part in softening agent;
1.6～2 parts of lubricants; 4～8 parts of properties-correcting agent;
1～3 part of compatilizer; 2～3 parts of coupling agents;
1～5 part of hyper-dispersant; 1～4 part of cats product;
1～1.8 part of whipping agent; 1～5 part of frothing aid;
0.3～1.2 part in oxidation inhibitor; 1～10 part of linking agent;
1～20 part of nucleator; 0.8～1 part of viscosity-depression agent;
0.8～1 part of tackifier; 3.2～13.4 parts of other auxiliary agents;
Wherein,
Described thermo-stabilizer is organotin stabilizer, calcium zinc stabilizer or lead salt one package stabilizer;
Described properties-correcting agent is ACR-401, Injecatable EVA Copolymer or chlorinatedpolyethylene;
Described cats product is a quaternary ammonium salt cationic surfactant;
Described whipping agent is sodium hydrogencarbonate and Cellmic C 121 or the fine combination of azo two isobutyls;
Described nucleator is a kind of or two or more combination arbitrarily that is selected from calcium carbonate crystal whisker, nano active light calcium carbonate, talcum powder, titanium oxide and the calcium stearate;
Described other auxiliary agent by weight, it consists of 0.5～1.2 part of 0.5～3 part in sodium hydroxide, 1～5 part in urea, 1～3 part of Paraformaldehyde 96,0.2～1.2 part in formic acid and trimeric cyanamide.
2. macromolecular fibre composite material according to claim 1 is characterized in that: the weight part of each component is:
50～100 parts of vegetable fibre fillers; 60～80 parts of plastic basis materials;
4～5 parts of thermo-stabilizers; 1～2 part in softening agent;
1.8～2 parts of lubricants; 5～7.5 parts of properties-correcting agent;
1.5～3 parts of compatilizers; 2～3 parts of coupling agents;
2～4 parts of hyper-dispersants; 1～2 part of cats product;
1.2～1.6 parts of whipping agents; 2～5 parts of frothing aids;
0.5～1 part in oxidation inhibitor; 1～5 part of linking agent;
5～13 parts of nucleators; 0.8～0.9 part of viscosity-depression agent;
0.8～0.9 part of tackifier; 4.7～6.7 parts of other auxiliary agents.
3. according to claim 1 or 2 described macromolecular fibre composite materials, it is characterized in that: described softening agent is one or more the combination that is selected from DOP, Witcizer 300 and the epoxy soybean oil.
4. according to claim 1 or 2 described macromolecular fibre composite materials, it is characterized in that: described lubricant is to be selected from a kind of or two or more combination arbitrarily in cured of Triple Pressed Stearic Acid, lead stearate, barium stearate, Zinic stearas, paraffin, polyethylene wax and oxidic polyethylene.
5. according to claim 1 or 2 described macromolecular fibre composite materials, it is characterized in that: described compatilizer is Vilaterm lactone, maleic anhydride, vinylformic acid or gathers the methylpropanoic acid formicester.
6. according to claim 1 or 2 described macromolecular fibre composite materials, it is characterized in that: described coupling agent is a kind of or two or more combination arbitrarily that is selected from silane coupling agent, titanate coupling agent and the aluminate coupling agent.
7. according to claim 1 or 2 described macromolecular fibre composite materials, it is characterized in that: described linking agent Lucidol, Di Cumyl Peroxide 99 or peroxidized t-butyl perbenzoate.
8. according to claim 1 or 2 described macromolecular fibre composite materials, it is characterized in that: described viscosity-depression agent is viscosity-depression agent LJ-950.
9. macromolecular fibre composite material according to claim 1 and 2 is characterized in that: described tackifier are polystyrene resin, mono-laurate polyoxyethylene compound or ethylene oxide-propylene oxide block copolymer.
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