CN100413926C - Environment friendly lignin foaming material and its contour machining process - Google Patents
Environment friendly lignin foaming material and its contour machining process Download PDFInfo
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- CN100413926C CN100413926C CNB2004100408981A CN200410040898A CN100413926C CN 100413926 C CN100413926 C CN 100413926C CN B2004100408981 A CNB2004100408981 A CN B2004100408981A CN 200410040898 A CN200410040898 A CN 200410040898A CN 100413926 C CN100413926 C CN 100413926C
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Abstract
The present invention relates to an environment-friendly lignin foaming material and a forming technology thereof, which belongs to the technical field of lignin material compounds. The environment-friendly lignin foaming material comprises the components according to the proportion by weight of 30 to 80 portions of high-pure lignin, 0 to 60 portions of resin, 1 to 10 portions of grafting modification object, 0 to 5 portions of initiating agent, 1 to 5 portions of foaming agent and 1 to 5 portions of lubricant. The forming technology comprises four steps that raw materials are processed, and the high-pure lignin is separated and purified; the components are metered according to the proportion by weight; the components are uniformly mixed in a high-speed mixing machine; an extruder is used for extruding the components at the temperature of 100 to 200 DEG C under the pressure of 0.1 to 1MPa after the components are melted and mixed together for 3 to 10 min at the temperature of 100 to 200 DEG C under the condition of 30 to 100 rpm; the components are formed, cooled and formed by a foaming mold or put in an injection machine or a heat pressing molding machine for forming in a foaming way. The environment-friendly lignin foaming material having the advantages of low-density, high intensity, favorable performance of thermal insulation and sound isolation, good temperature retention, shock resistance, easy forming, easy degradation, etc. can be widely used in the fields of cushioning packaging, packaging for food fresh keeping, heat insulation for inner and outer walls, thermal insulation, articles of daily use, etc.
Description
(1) technical field
The present invention relates to eco-friendly lignin foam material and contour machining procedure thereof, belong to the composition that contains lignin material.Be the modification and the novel material exploitation of natural lignin.
(2) background technology
On the earth natural plant material-lignin next in number only to Mierocrystalline cellulose, estimate that the annual whole world can produce 1,500 hundred million tons of lignins by plant-growth.The history in existing several thousand of human use's Mierocrystalline cellulose, and lignin really to begin one's study be thing after nineteen thirty, and well do not utilize so far, the Nature offers human large resource, wasted every year.In the essence cellulosic material three big components, have only lignin not obtain effectively to utilize, and become obstacle and the environmental pollutant of related industries in using, so the utilization of lignin resource still is that the human social angle sees that meaning is all very great from the nature Carbon cycle.
The foams plastic material thermal conductivity is low, in light weight, easy construction, use in fields such as heat insulation, insulation, food, buildings is more and more, but commonly used as foam materialss such as urethane, polystyrene, polyethylene exist easy firing, the amount of being fuming is big, heat resisting temperature is low, particularly shortcoming such as poor, contaminate environment of waste degradation property has been subjected to increasing restriction in actual applications.With reproducible native lignin is main raw material development environment close friend's lignin foam material, in foaming and moulding process, have excellent high-temperature tensile property, dynamic mechanical, mechanical property, and can degrade fully under physical environment (light, heat, microorganism etc.) condition, its degraded can be controlled inductive phase.Product after the forming process has the characteristics of light weight, specific tenacity height, waterproof, anticorrosion, insulation, can be widely used in building, transportation, packing, home decoration and daily necessities market.
(3) summary of the invention
1, to the purpose of this invention is to provide a kind of be raw material with the native lignin to goal of the invention, and the method for production environment close friend's lignin foam material is the service that large-scale develops and utilizes of renewable resources native lignin.
2, technical scheme technical scheme of the present invention is: with weighing by weight ratio and high-speed mixing such as high purity lignin, resin, graft modification thing, initiator, whipping agent, lubricants; Again above-mentioned batching is inserted the forcing machine melt blending, extrude,, or drop into foaming in injector or the hot-die molding machine through foaming mould foaming cooling and shaping with forcing machine.Promptly obtain eco-friendly lignin foam material and product.
Each component is by weight: high purity lignin 30～80, resin 20～60, graft modification thing 5～7, initiator 1～5, whipping agent 2～5, lubricant 2～5.
The lignin that high purity lignin is handled, purified by organic solvent.Utilize lignin to be dissolved in organic solvent and in organic solvent, be easy to the cohesion, the polymeric characteristic, black, red liquid that organic solvent slurrying, alkaline process, sulfite pulping, the slurrying of imido method, mechanical feedback, biological process slurrying are obtained, after concentrating, the ratio in 1: 1～10 adds hot organic solvent; Raw material is the general industry lignin products, then add hot organic solvent stirring and dissolving in 1: 1～6 ratio after, centrifugal or remove by filter impurity, distillation obtains high purity lignin after reclaiming organic solvent, molecular weight＞more than 1000, purity＞more than 60%, second-order transition temperature＞100 ℃.
The organic solvent of the high-purity art element of described extraction is selected dioxane, acetyl bromide and derivative for use; Methyl alcohol, ethanol, hexafluoro propyl alcohol class and derivative; Acetone, butanone class and derivative; Formic acid, acetate, propionic acid class and derivative; Ethyl formate, ethyl acetate class and derivative; Lower paraffin hydrocarbons hydramine and derivative; The single solvent or the double solvents of ammonia, ammoniacal liquor etc. and ammonium salt class.
Resin is selected new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE), polyvinyl chloride (PVC), polypropylene (PP), urethane (PU), polystyrene (PA) or resol (PF) for use; And ethylene/vinyl acetate multipolymer (EVA), ethylene/ethyl acrylate multipolymer (EEA), one or more arbitrary combination in the ethylene/acrylic acid copolymer (EAA).
The graft modification thing is selected hendecene base Succinic anhydried, undecane diacid, hendecene base Succinic anhydried, dodecenylsuccinic acid ester, octadecenic acid, poly(lactic acid), 6 hydroxycaproic acid, 1 for use, 2,3,4-suberane tetracarboxylic acid, 1,2,3, the arbitrary combination of one or more in 4-tetramethylene tetracarboxylic acid acids and the ester class thereof.
Initiator is selected benzoyl peroxide, lauroyl peroxide, chloro benzoyl peroxide, acetyl peroxide, cumene peroxide, a for use, a '-two (t-butyl peroxy di-isopropyl) benzene, ditertiary butyl peroxide, 2,5-(t-butyl peroxy) hexane, 1,1-t-butyl peroxy-3,3,5-trimethyl-cyclohexane, t-butyl peroxy pivalate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy benzoic ether, two (4-tert-butylcyclohexyl) peroxide two carbonic ethers, diisopropyl peroxydicarbonate, BPIC (t butyl peroxy isopropyl carbonate); With one or more the arbitrary combination in the azobis isobutyronitrile class.
Whipping agent is selected pneumatogen or chemical foaming agent for use, as yellow soda ash, sodium bicarbonate, CO
2, the one or more kinds of arbitrary combination in the Cellmic C 121, Diisopropyl azodicarboxylate.
Lubricant is selected the one or more kinds of arbitrary combination in paraffin, stearic acid, polyethylene wax or the oxidic polyethylene for use.
With above-mentioned each component mixing in high-speed mixer by weight ratio; With forcing machine prior to melt blending 3～10min under 100～200 ℃, 10～80rpm condition, under 110～210 ℃, 0.1～1MPa, extrude then, through foaming mould foaming cooling and shaping, or drop into foaming in injector or the hot-die molding machine, promptly obtain eco-friendly lignin foam material and product.
3, beneficial effect with lignin modified, increases its relative molecular mass by melt blending, and shape of molecule is converted into linear polymers by Einstein ball and closely curling body, makes it help graft copolymerization, strengthens film forming, network-like plasticity and controlled release characteristics.With a series of excellent properties that lignin had,, in the melt blending modification, reproduced and superposeed as biological degradation, graft copolymerization, vitrifying film forming, absorption slowly-releasing etc.Lignin materials processing after the melt blending modification is functional, and under the effect of whipping agent, uniform in foaming is stable, it is good that multiplying power height, goods melt knot property, the intensity height, pore is evenly distributed tiny, has good resistance destructiveness and anti-seismic performance, and good heat preservation and soundproof performance.Have after eco-friendly lignin is foaming material shaped that density is low, intensity is high, sound deadener/insulator is good, good heat preservation performance, shockproof, easy-formation, easy advantage such as degraded, in buffering package, food fresh keeping packing, fields such as inside and outside wall thermal insulation, heat insulation, building industry, agricultural and daily necessities will be widely used.
(4) embodiment
Below in conjunction with embodiment the present invention is described in further details.
High purity lignin produce 1: get black, red liquid that the imido method obtains, heating is concentrated into Baume more than 20 °, ratio in 1: 1～8 adds 50 ℃ ethyl acetate, heat after the airtight stirring to 80 ℃, leave standstill cooling 2 hours, after the liquid layering to be mixed, remove the impurity of bottom, ethyl acetate is reclaimed in upper strata liquid distillation, and the solid substance that obtains is high purity lignin after drying.Molecular weight＞more than 1000, purity＞more than 60%, second-order transition temperature＞100 ℃, moisture＜1%.
High purity lignin produce 2: getting industrial lignin is raw material, dioxane in 90 ℃ of 1: 6 ratio addings, add HCl and regulate pH＜6, heat after the airtight stirring to 100 ℃, leave standstill cooling 2 hours, after the liquid layering to be mixed, remove the impurity of bottom, ethyl acetate is reclaimed in upper strata liquid distillation, and the solid substance that obtains is high purity lignin after drying.Molecular weight＞more than 1000, purity＞more than 60%, second-order transition temperature＞100 ℃, moisture＜1%.
Embodiment 1 gets high-purity element 40, new LDPE (film grade) 20, hendecene base Succinic anhydried 5, benzoyl peroxide 1, Cellmic C 121 5, whiteruss 2 mixing in high-speed mixer by weight; , under 110 ℃, 0.4MPa, extrude then prior to melt blending 5min under 140 ℃, 30rpm condition with forcing machine,, promptly obtain eco-friendly lignin foam material and moulding product through foaming mould foaming cooling and shaping.
Embodiment 2: get high purity lignin 60, polyvinyl chloride 50, octadecenic acid 6, lauroyl peroxide 3, Diisopropyl azodicarboxylate 5, polyethylene wax 5 mixing in high-speed mixer by weight; , under 110 ℃, 0.4MPa, extrude then prior to melt blending 5min under 160 ℃, 50rpm condition with forcing machine, drop into foaming in the injector, promptly obtain eco-friendly lignin foam material and moulding product.
Embodiment 3: get high purity lignin 80, polystyrene 60, dodecenylsuccinic acid ester 7, dicumyl peroxide 5, Cellmic C 121 3, yellow soda ash 2, stearic acid 4 mixing in high-speed mixer by weight; , under 110 ℃, 0.4MPa, extrude then prior to melt blending 5min under 200 ℃, 40rpm condition with forcing machine, drop into foaming in the hot-die molding machine, promptly obtain eco-friendly lignin foam material and moulding product.
Above-mentioned lignin foam material and processing and forming technology, because foam material and mould can be progressively releasing pattern, the die gap magnification is from 0.5～20 times, various foamed profile desired density decision burst sizes according to different purposes, the extrusion foaming material is through the cooling and shaping sync pulling, customized cut-off becomes desired size, and foam material density is at 10～50kg/m
3Between.
Claims (7)
1. eco-friendly lignin foam material comprises high purity lignin, resin, graft modification thing, initiator, whipping agent, lubricant; It is characterized in that, described each component of lignin foam material is by weight: molecular weight＞1000, purity＞60%, second-order transition temperature＞100 ℃, the high purity lignin 30～80 of moisture＜1%, resin 40～60, graft modification thing 5～7, initiator 1～5, whipping agent 2～5 and lubricant 2～5; Described graft modification thing is selected hendecene base Succinic anhydried, undecane diacid, dodecenylsuccinic acid ester, octadecenic acid, poly(lactic acid), 6 hydroxycaproic acid, 1,2,3 for use, 4-suberane tetracarboxylic acid, 1,2,3, the arbitrary combination of one or more in 4-tetramethylene tetracarboxylic acid and the ester thereof; With the material for preparing with forcing machine prior to melt blending 3～10min under 100～200 ℃, 30～100rpm condition; Under 110～210 ℃, 0.1～1MPa, extrude again,, or drop into that foaming gets product in injector or the hot-die molding machine through foaming mould foaming cooling and shaping.
2. eco-friendly lignin foam material according to claim 1, it is characterized in that described resin is selected new LDPE (film grade), linear low density polyethylene, high density polyethylene(HDPE), polyvinyl chloride, polypropylene, urethane, polystyrene or resol for use; And the ethylene/vinyl acetate multipolymer, ethylene/ethyl acrylate multipolymer, one or more arbitrary combination in the ethylene/acrylic acid copolymer.
3. eco-friendly lignin foam material according to claim 1, it is characterized in that described initiator is selected benzoyl peroxide, lauroyl peroxide, chloro benzoyl peroxide, acetyl peroxide, cumene peroxide, ditertiary butyl peroxide, t-butyl peroxy pivalate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy benzoic ether, two (4-tert-butylcyclohexyl) peroxide two carbonic ethers, diisopropyl peroxydicarbonate, BPIC (t butyl peroxy isopropyl carbonate) for use; With one or more the arbitrary combination in the Diisopropyl azodicarboxylate.
4. eco-friendly lignin foam material according to claim 1 is characterized in that whipping agent is selected yellow soda ash, sodium bicarbonate, CO for use
2, the one or more kinds of arbitrary combination in the Cellmic C 121, Diisopropyl azodicarboxylate.
5. eco-friendly lignin foam material according to claim 1 is characterized in that lubricant is selected the one or more kinds of arbitrary combination in paraffin, stearic acid, polyethylene wax or the oxidic polyethylene for use.
6. the method for processing forming of environmental friendliness lignin foam material according to claim 1 the steps include:
The first step, the preparation high purity lignin, utilize lignin to be dissolved in organic solvent, and in organic solvent, be easy to cohesion, the polymeric characteristic, with organic solvent slurrying, alkaline process, sulfite pulping, the slurrying of imido method, black liquor that mechanical feedback or biological process slurrying obtain or red liquid, be concentrated into Baume more than 20 °, after adding hot organic solvent stirring and dissolving in the ratio of lignin and organic solvent 1: 1～10, centrifugal or remove by filter impurity, distillation obtains high purity lignin after reclaiming organic solvent, molecular weight＞1000, purity＞60%, second-order transition temperature＞100 ℃, moisture＜1%;
In second step, batching is got high purity lignin 30～80, resin 40～60, graft modification thing 5～7, initiator 1～5, whipping agent 2～5, lubricant 2～5, mixing in high-speed mixer by weight ratio;
The 3rd step, with the material for preparing with forcing machine prior to melt blending 3～10min under 100～200 ℃, 30～100rpm condition;
The 4th step, under 110～210 ℃, 0.1～1MPa, extrude, through foaming mould foaming cooling and shaping, or drop into foaming in injector or the hot-die molding machine.
7. the method for processing forming of eco-friendly lignin foam material according to claim 6, it is characterized in that the organic solvent of preparation high purity lignin is selected single solvent or the double solvents in dioxane, acetyl bromide, methyl alcohol, ethanol, hexafluoro propyl alcohol, acetone, butanone, formic acid, acetate, propionic acid, ethyl formate, ethyl acetate, the lower paraffin hydrocarbons hydramine for use.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100408981A CN100413926C (en) | 2004-10-25 | 2004-10-25 | Environment friendly lignin foaming material and its contour machining process |
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| CNB2004100408981A CN100413926C (en) | 2004-10-25 | 2004-10-25 | Environment friendly lignin foaming material and its contour machining process |
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| CN100413926C true CN100413926C (en) | 2008-08-27 |
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| CN103756090A (en) * | 2014-01-06 | 2014-04-30 | 大连工业大学 | Method for preparing high specific strength polyethylene/alkali lignin foam material |
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| CN109694531A (en) * | 2018-12-20 | 2019-04-30 | 上海昶法新材料有限公司 | A kind of PVC/ papermaking waste fretting map composite material and preparation method |
| CN110920018A (en) * | 2019-11-21 | 2020-03-27 | 佛山碧嘉高新材料科技有限公司 | Polylactic acid foaming method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125738A (en) * | 1994-12-28 | 1996-07-03 | 濮阳天安企业集团 | Decorative material and its manufacture method |
| CN1262644A (en) * | 1997-05-13 | 2000-08-09 | 杜邦-Mrc株式会社 | Wood-like molding, process for preparing same, and composition for molding |
| CN1356867A (en) * | 1999-06-22 | 2002-07-03 | 希乐克公司 | Texturized cellulosic and lignocellulosic materials and compositions and composites made therefrom |
| CN1465623A (en) * | 2002-06-21 | 2004-01-07 | 张惠民 | Environment protection type lignin fog-film |
-
2004
- 2004-10-25 CN CNB2004100408981A patent/CN100413926C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125738A (en) * | 1994-12-28 | 1996-07-03 | 濮阳天安企业集团 | Decorative material and its manufacture method |
| CN1262644A (en) * | 1997-05-13 | 2000-08-09 | 杜邦-Mrc株式会社 | Wood-like molding, process for preparing same, and composition for molding |
| CN1356867A (en) * | 1999-06-22 | 2002-07-03 | 希乐克公司 | Texturized cellulosic and lignocellulosic materials and compositions and composites made therefrom |
| CN1465623A (en) * | 2002-06-21 | 2004-01-07 | 张惠民 | Environment protection type lignin fog-film |
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