CN104804225A - Method for surface hydroxyl modification of starch and cellulose solid powder - Google Patents
Method for surface hydroxyl modification of starch and cellulose solid powder Download PDFInfo
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Abstract
The invention provides a method for surface hydroxyl modification of starch and cellulose (plant straw) solid powder and belongs to the technical field of bio-based materials. The starch or the cellulose solid powder and a catalyst are jointly put in a high-speed stirrer and stirred for a reaction, and modified starch or modified cellulose is obtained; the starch or the cellulose solid powder, the catalyst, polyolefin and a processing aid are jointly put in the high-speed stirrer and stirred for a reaction, and a blended material of the modified starch or the modified cellulose and polyolefin is obtained; the catalyst is one or more of a metal fatty acid catalyst, a heteropoly acid catalyst and a metal ester compounded catalyst. According to the modification method, media and solvents are not required, the operation is simple and convenient, and the blending compatibility of the starch and the cellulose solid powder with polyolefin, aliphatic polyester and other synthetic macromoleclar polymers can be improved after modification, so that the mechanical property of bio-based plastics is improved; meanwhile, the content of biomass in bio-based plastics is increased.
Description
Technical field
The invention belongs to bio-based materials technical field, be specifically related to a kind of method of starch, Mierocrystalline cellulose (straw) solid powder surfaces hydroxyl modification.
Background technology
Current mankind society is faced with and saves Energy resources, reduces Carbon emission, sets up many social concerns such as the society of Sustainable development, at plastic industry, and the problem that research and development utilize biomass resource, Developing Biomass plastics have just become countries in the world to pay close attention to.Current domestic and international market has occurred that some are manufactured " bio-based plastics " by starch and polyolefin blend.These " bio-based plastics " have employed part biological raw material-W-Gum and instead of part petroleum resources, but because the phase behavior of starch is polar phase in this " bio-based plastics ", and polyolefinic phase behavior is nonpolar phase, reciprocal compatibility is poor, therefore starch content lower (about containing less than 30%) in this " bio-based plastics " blend, otherwise the mechanical property of blend " bio-based plastics " obviously declines.In order to promote the starch content (and not reducing the mechanical property of plastics) in starch and polyolefinic consistency, raising " bio-based plastics ", researchist has made numerous effort.
University Of Ji'nan Meng Ping stamens etc. (application number: 201310311471.X) adopt ultra-sonic oscillation process starch, add coupling agent again and microspheroidal height hydrophobic starch particle prepared by hydrophobizing agent, and prepare calendered film with PVC blending and modifying and prepare cast film with PVA blending and modifying.
Wuhan Huali Environmental Protection Science and Technology Co., Ltd Pan Li is beautiful, Hu Hanjie etc. (application number: 201210388056.X) discloses " matrix material of a kind of starch and poly(lactic acid) and preparation method thereof ", starch, poly(lactic acid), terminal hydroxy group lactic acid oligomer, softening agent, talcum powder, lubricant, coupling agent is first blended, then add chainextender obtains starch and poly(lactic acid) matrix material through twin-screw extrusion.
200710049748.0) etc. Yuan Minglong (application number: disclose " coupling of Biodegradable polylactic acid/starch compound material coblended interface and capacity increasing technique ", by blending and modifyings such as poly(lactic acid), starch, expanding material, coupling agent, processing aids, obtain PLA/Starch Blends through twin-screw extrusion; Above unit and scholar adopt the way of adding compatilizer and coupling agent, apply for above-mentioned patent, this technology can improve the consistency of the synthetic polymer such as starch and polyolefine, but compatilizer and coupling agent can not add too much, otherwise the mechanical property of impact " bio-based plastics ", also can increase the cost of " bio-based plastics ".
Southern Yangtze University (CN102030833A) Zhang Yanping, Hu Yanan etc. disclose " preparation method of the starch ester of a kind of natural oil and starch esterification ", take starch as raw material, natural oil is esterifying agent, the dry process be combined with heat with microwave carries out acidolysis and esterification modification to starch, prepares the starch fat prod of low degree of substitution.
Jilin Agriculture University Liu Jun plum, recklessly to shine etc. (application number: 201310130369.X) disclose " a kind of modification buckwheat starch and preparation method thereof ", by sizing mixing to buckwheat starch, being cross-linked, the technique such as esterification, prepared modification buckwheat.
Guangzhou University's (application number: 201310487376.5) Shang little Qin etc. disclose " a kind of preparation method of composite modified high amylose starch ", first adopt esterifying agent dodecenylsuccinic anhydride to carry out esterification modification to the high amylose starch that amylose content is 50 ~ 85wt%, obtain starch ester; Adopt etherifying agent propylene oxide to carry out etherification modified to starch ester again, obtain composite modified high amylose starch, this modification technology can increase the cost of starch.
Guangxi State Farms Mingyang Biochemical Group, Inc. (CN 103044718 A) Xie Xiaoming etc. discloses " a kind of starch-based degradable plastics and preparation method thereof ", tapioca (flour) is first added oxyhydroxide activation treatment, add esterifying agent, coupling agent, ethylene/acrylic acid copolymer, ethylene/vinyl alcohol copolymer, polyvinyl alcohol, softening agent and other auxiliary agent etc. more blended, prepare starch-based degradable plastics.
Beijing Forestry University (CN 102311550 A) Yuan Tongqi etc. discloses the preparation method of " a kind of lignocellulose Esterification modification method and esterification modification lignocellulose ", in a heated state lignocellulose is dissolved in imidazolium ionic liquid, add acid binding agent and esterifying reagent again, carry out esterification and prepare modification lignocellulose, this modification technology obviously can increase cellulosic cost.
Guangxi University's (application number: 201310320367.7) yellow Zu Qiang etc. have applied for " a kind of cellulose fatty acid ester and preparation method thereof ", by the technology of the heatable catalytic esterification modification in ball mill such as stalk cellulose powder and lipid acid, acid anhydrides, Tosyl chloride, trichoroacetic acid(TCA) acid anhydrides, this modification technology does not have medium, easy and simple to handle, but the gamma value of cellulose powder is lower, and add the modified washing step of stalk cellulose powder, be unfavorable for industrialization.
Southern Yangtze University Zhang Yanping, Liu Li (CN101824094A) have applied for the patent of " a kind of preparations and applicatio of fatty acid starch ester by drum process ", employing starch is raw material, lipid acid is esterifying agent, under the condition of roller dryer as chemical reactor, esterification modification is carried out to starch, has prepared fatty acid starch ester.This modification technology does not have medium, easy and simple to handle, but the gamma value of starch is lower, and hydrochloric, the vitriol oil or acetic acid are introduced in " bio-based plastics ", corrosive nature may be had to equipment in the processing of follow-up screw rod, and due to the existence of inorganic acid, during with this esterification starch and the blended preparation of aliphatic polyester other " bio-based plastics ", the degraded of aliphatic polyester may be caused.
For improving the deficiency of the biomass modified method such as above-mentioned starch, cellulose solids powder, the invention provides the modification technology of the online solid phase to biomass such as starch, cellulose solids powder, catalyst etherifying, esterification.
Summary of the invention
The invention provides a kind of method of starch, cellulose solids powder surface hydroxyl modification, the modified consistency improving starch, cellulose solids powder and synthesising macromolecule copolymer, thus improve the mechanical property of " bio-based plastics ", improve the content of biomass in " bio-based plastics " simultaneously.
The invention provides a kind of starch, cellulose solids powder surface hydroxyl modification method, starch or cellulose solids powder are invested in homogenizer together with catalyzer, stir, react, obtain treated starch or modified-cellulose; Or starch or cellulose solids powder, catalyzer, polyolefine are invested in homogenizer together with processing aid, to stir, reaction, obtain treated starch or modified-cellulose and polyolefinic blended batching; Described catalyzer be metal fatty acid salt, heteropolyacid, metal ester class catalyst compounded in one or more.
Preferably, described starch is W-Gum, tapioca (flour), potato starch or pea starch, and described cellulose solids powder is corn stalk powder, cotton stalk powder, rape straw, Chinese hemp stalk powder, rice straw powder, weeds powder, husk powder, bagasse powder or bamboo powder; The particle diameter of described cellulose solids powder is less than 200 orders.
Preferably, in described metal fatty acid salt, metal is magnesium, iron, zinc, calcium or rare earth, and described lipid acid is acetic acid, propionic acid, butyric acid, citric acid, stearic acid, Palmiticacid, oleic acid or lauric acid; Described metal ester class is titanic acid ester or Aluminate; Described heteropolyacid is phospho-wolframic acid or phospho-molybdic acid.
Preferably, described rare earth is cerium, neodymium, yttrium or mishmetal.
Preferably, when starch or cellulose solids powder being invested in homogenizer together with catalyzer, described temperature of reaction is 120-190 DEG C.
Preferably, when starch or cellulose solids powder, catalyzer, polyolefine being invested in homogenizer together with processing aid, described temperature of reaction is 120-190 DEG C.
Preferably, when starch or cellulose solids powder being invested in homogenizer together with catalyzer, the described reaction times is 15-45 minute.
Preferably, when starch or cellulose solids powder, catalyzer, polyolefine being invested in homogenizer together with processing aid, the described reaction times is 15-45 minute.
Preferably, when starch or cellulose solids powder being invested in homogenizer together with catalyzer, described catalyst content is the 0.5-8% of starch or cellulose solids powder and total catalyst weight.
When starch or cellulose solids powder, catalyzer, polyolefine being invested in homogenizer together with processing aid, described catalyst content is the 0.5-8% of starch or cellulose solids powder, catalyzer, polyolefine and processing aid gross weight.
Beneficial effect of the present invention:
Method of modifying of the present invention does not need medium, does not need solvent, easy and simple to handle, does not increase manufacturing procedure, cost increases few, is a kind of online method of modifying for plastic working.Starch or cellulose solids powder are invested in homogenizer together with catalyzer, or starch or cellulose solids powder, catalyzer, polyolefine are invested in homogenizer together with processing aid, stir, react, obtain treated starch or Mierocrystalline cellulose (or and polyolefinic blended batching).Period, the hydroxyl on the powdered biomass surfaces such as starch, cellulose solids powder reacts each other under catalyst action, dehydration, form ehter bond, or and plastic formula processing aid component in carboxyl reaction, dehydration, formed ester group, thus reach the oh group that the powdered biomass such as starch, cellulose powder solid surface is even eliminated in minimizing, powdered biomass solid surface from polar-modified be nonpolar object.
Modified starch, the powdered biomass solid surface such as plant straw powder have been apolar surfaces, because this increasing and polypropylene, polyethylene, the interface compatibility of the synthetic polymers such as aliphatic polyester, thus improve starch, the mechanical property of the powdered biomass such as cellulose powder-synthetic polymer polyblend, improve starch in blend plastics simultaneously, the content of the biomass such as plant straw powder and reducing costs, this treated starch and modified-cellulose powder are extruded at thermoplastic, in blown film and standby " bio-based plastics " of injection molding legal system, its content can reach 40%-80%.
Embodiment
The method of a kind of starch provided by the invention, cellulose solids powder surface hydroxyl modification, is invested in starch or cellulose solids powder in homogenizer together with catalyzer, stirs, reacts, obtain treated starch or modified-cellulose; Or starch or cellulose solids powder, catalyzer, polyolefine are invested in homogenizer together with processing aid, to stir, reaction, obtain treated starch or modified-cellulose and polyolefinic blended batching; Described catalyzer be metal fatty acid salt, heteropolyacid, metal ester class catalyst compounded in one or more.Wherein, polyolefine conventional in the plastic working that described polyolefine and processing aid are well known to those skilled in the art and processing aid, described polyolefine preferably uses polypropylene, and described processing aid preferably uses bisphenol A type epoxy resin.
For making those skilled in the art understand technical scheme of the present invention better, be described in further detail the present invention below in conjunction with specific embodiment, protection scope of the present invention is not limited by the following examples.The homogenizer used in the present invention is homogenizer conventional during plastic working, and the present invention does not have special restriction to this.
Example 1
First by following mass ratio configuration composite catalyst: iron stearate 40%, Aluminate (distearyl acyl-oxygen sec.-propyl Aluminate) 40%, stearic acid 20%, in container a little heat, stir, mix stand-by.Prepare burden according to the following formulation again: W-Gum 94%, composite catalyst 6%.Above-mentioned batching is invested in height stirs in machine, and in 170 DEG C, high-speed stirring 40 minutes, has a large amount of steam to discharge always, react complete for subsequent use in high-speed agitating process.In modified starch infrared spectrum wave number be 3400 hydroxyl peak area about reduce 40%, modified starch is hydrophobic in nature.
Example 2
First by following mass ratio configuration composite catalyst: Zinic stearas 40%, Aluminate (distearyl acyl-oxygen sec.-propyl Aluminate) 40%, oleic acid 20%, in container a little heat, stir, mix stand-by.Prepare burden according to the following formulation again: W-Gum 93%, composite catalyst 7%.Above-mentioned batching is invested in height stirs in machine, and in 140 DEG C, high-speed stirring 30 minutes, has a large amount of steam to discharge always, react complete for subsequent use in high-speed agitating process.In modified starch infrared spectrum wave number be 3400 hydroxyl peak area about reduce 25%, modified starch is hydrophobic in nature.
Example 3
First by following mass ratio configuration composite catalyst: calcium stearate 40%, tetrabutyl titanate 40%, citric acid 20%, in container a little heat, stir, mix stand-by.Prepare burden according to the following formulation again: W-Gum 92%, composite catalyst 8%.Above-mentioned batching is invested in height stirs in machine, and in 150 DEG C, high-speed stirring 40 minutes, has a large amount of steam to discharge always, react complete for subsequent use in high-speed agitating process.In modified starch infrared spectrum wave number be 3400 hydroxyl peak area about reduce 30%, modified starch is hydrophobic in nature.
Example 4
First by following mass ratio configuration composite catalyst: iron stearate 40%, tetrabutyl titanate 40%, stearic acid 20%, in container a little heat, stir, mix stand-by.Prepare burden according to the following formulation again: W-Gum 93%, composite catalyst 7%.Above-mentioned batching is invested in height stirs in machine, and in 130 DEG C, high-speed stirring 30 minutes, has a large amount of steam to discharge always, react complete for subsequent use in high-speed stirring.In modified starch infrared spectrum wave number be 3400 hydroxyl peak area about reduce 25%, modified starch is hydrophobic in nature.
Example 5
First by following mass ratio configuration composite catalyst: Zinic stearas 40%, tetrabutyl titanate 40%, lauric acid 20%, in container a little heat, stir, mix stand-by.Prepare burden according to the following formulation again: W-Gum 92%, composite catalyst 8%.Above-mentioned batching is invested in height stirs in machine, and in 160 DEG C, high-speed stirring 40 minutes, has a large amount of steam to discharge always, react complete for subsequent use in high-speed stirring.In modified starch infrared spectrum wave number be 3400 hydroxyl peak area about reduce 36%, modified starch is hydrophobic in nature.
Example 6
First by following mass ratio configuration composite catalyst: cerium stearate 40%, Aluminate (distearyl acyl-oxygen sec.-propyl Aluminate) 40%, stearic acid 20%, in container a little heat, stir, mix stand-by.Prepare burden according to the following formulation again: W-Gum 92%, composite catalyst 8%.Above-mentioned batching is invested in height stirs in machine, and in 140 DEG C, high-speed stirring 30 minutes, has a large amount of steam to discharge always, react complete for subsequent use in high-speed agitating process.In modified starch infrared spectrum wave number be 3400 hydroxyl peak area about reduce 25%, modified starch is hydrophobic in nature.
Respectively the treated starch prepared by example 1-6 is tested mechanical property by the blended processing of following formula rate: treated starch 48%, powdered polypropylene 50%, bisphenol A type epoxy resin 2%, extrude through parallel equidirectional two-screw forcing machine, screw rod each district processing temperature is respectively: a district 100-130 DEG C, two district 140-150 DEG C, three district 160-170 DEG C, four district 160-170 DEG C, five district 150-170 DEG C, six district 150-160 DEG C, seven district 150-160 DEG C, eight district 150-160 DEG C, nine district 140-150 DEG C, head 140-150 DEG C, screw speed is 50-400 rev/min.Extrude material strip through air-cooled tie rod pelletizing, 60 DEG C of forced air dryings 8 hours, the mechanical property of the blending resin obtained lists in table 1.
Example 7
First by following mass ratio configuration composite catalyst: heteropolyacid (model HPW-12) 40%, Aluminate (distearyl acyl-oxygen sec.-propyl Aluminate) 40%, oleic acid 20%, in container a little heat, stir, mix stand-by.Again according to the following formulation and ratio batching: W-Gum 45%, composite catalyst 5%, powdered polypropylene 48%, bisphenol A type epoxy resin 2%, is invested in height together by above-mentioned recipe ingredient and stirs in machine, in 150 DEG C, high-speed stirring 40 minutes, has a large amount of steam to discharge always, reacts complete and extrude through parallel equidirectional two-screw forcing machine in high-speed stirring, processing condition are with example 1-6, and the mechanical property of the blending resin obtained lists in table 1.Get modified, enter twin screw before treated starch in formulation material do infrared spectrum, in spectrogram wave number be 3400 hydroxyl peak area about reduce 40%, modified starch is hydrophobic in nature.
Example 8
First by following mass ratio configuration composite catalyst: Zinic stearas 40%, Aluminate (distearyl acyl-oxygen sec.-propyl Aluminate) 40%, oleic acid 20%, in container a little heat, stir, mix stand-by.According to the following formulation and ratio batching: bamboo powder (particle diameter is less than 200 orders) 52%, composite catalyst 6%, one arises from 150 DEG C of high-speed stirring 40 minutes, and then adds following recipe ingredient: polypropylene 40%, bisphenol A type epoxy resin 2%, one arises from 150 DEG C of high-speed stirring 10 minutes again.Compound parallel equidirectional two-screw forcing machine is extruded, granulation, and processing condition are with example 1-6, and the mechanical property of the blending resin obtained lists in table 1.
Example 9
First by following mass ratio configuration composite catalyst: cerous acetate 40%, tetrabutyl titanate 40%, stearic acid 20%, in container a little heat, stir, mix stand-by.Again according to the following formulation and ratio batching: bamboo powder (particle diameter is less than 200 orders) 40%, composite catalyst 5%, one arises from 130 DEG C of high-speed stirring 40 minutes, and then add following recipe ingredient: polypropylene 53%, bisphenol A type epoxy resin 2%, one arises from 130 DEG C of high-speed stirring 10 minutes again.Compound parallel equidirectional two-screw forcing machine is extruded, granulation, and processing condition are with example 1-6, and the mechanical property of the blending resin obtained lists in table 1.
Example 10
In following quality when ratio batching: starch 47%, with powdered polypropylene 48%, silane coupling agent (KH560) 1%, bisphenol A type epoxy resin 2%, calcium stearate 2%, one arises from 150 DEG C of high-speed stirring 10 minutes, extrude through parallel equidirectional two-screw forcing machine, screw rod each district processing temperature is respectively: a district 100-130 DEG C, two district 140-150 DEG C, three district 160-170 DEG C, four district 160-170 DEG C, five district 150-170 DEG C, six district 150-160 DEG C, seven district 150-160 DEG C, eight district 150-160 DEG C, nine district 140-150 DEG C, head 140-150 DEG C, screw speed is 50-400 rev/min.Extrude material strip through air-cooled tie rod pelletizing, 60 DEG C of forced air dryings 8 hours, the mechanical property of the blending resin obtained lists in table 1.The mechanical property of bio-based plastics prepared by comparison example 1-9 and example 10 can be found out, by powdered biomass modification in advance, and then and the mechanical property of bio-based plastics of polypropene blended preparation have and increase significantly.
Table 1 starch, cellulose solids powder and PP blend mechanical property
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.Should be understood that, under the premise without departing from the principles of the invention, those skilled in the art can realize the present invention according to the suitable improving technique parameter of the present invention, but all similar replacements and change are all apparent for a person skilled in the art, and they are all deemed to be included in Seeking for Right of the present invention.
Claims (10)
1. a method for starch, cellulose solids powder surface hydroxyl modification, is characterized in that, starch or cellulose solids powder is invested in together with catalyzer in homogenizer, stirs, reacts, obtain treated starch or modified-cellulose; Or starch or cellulose solids powder, catalyzer, polyolefine are invested in homogenizer together with processing aid, to stir, reaction, obtain treated starch or modified-cellulose and polyolefinic blended batching; Described catalyzer be metal fatty acid salt, heteropolyacid, metal ester class catalyst compounded in one or more.
2. the method for a kind of starch according to claim 1, cellulose solids powder surface hydroxyl modification, it is characterized in that, described starch is W-Gum, tapioca (flour), potato starch or pea starch, and described cellulose solids powder is corn stalk powder, cotton stalk powder, rape straw, Chinese hemp stalk powder, rice straw powder, weeds powder, husk powder, bagasse powder or bamboo powder; The particle diameter of described cellulose solids powder is less than 200 orders.
3. the method for a kind of starch according to claim 1, cellulose solids powder surface hydroxyl modification, it is characterized in that, in described metal fatty acid salt, metal is magnesium, iron, zinc, calcium or rare earth, and described lipid acid is acetic acid, propionic acid, butyric acid, citric acid, stearic acid, Palmiticacid, oleic acid or lauric acid; Described metal ester class is titanic acid ester or Aluminate; Described heteropolyacid is phospho-wolframic acid or phospho-molybdic acid.
4. the method for a kind of starch according to claim 3, cellulose solids powder surface hydroxyl modification, is characterized in that, described rare earth is cerium, neodymium, yttrium or mishmetal.
5. the method for a kind of starch according to claim 1, cellulose solids powder surface hydroxyl modification, is characterized in that, when starch or cellulose solids powder being invested in homogenizer together with catalyzer, described temperature of reaction is 120-190 DEG C.
6. the method for a kind of starch according to claim 1, cellulose solids powder surface hydroxyl modification, it is characterized in that, when starch or cellulose solids powder, catalyzer, polyolefine being invested in homogenizer together with processing aid, described temperature of reaction is 120-190 DEG C.
7. the method for a kind of starch according to claim 1, cellulose solids powder surface hydroxyl modification, is characterized in that, when starch or cellulose solids powder being invested in homogenizer together with catalyzer, the described reaction times is 15-45 minute.
8. the method for a kind of starch according to claim 1, cellulose solids powder surface hydroxyl modification, it is characterized in that, when starch or cellulose solids powder, catalyzer, polyolefine being invested in homogenizer together with processing aid, the described reaction times is 15-45 minute.
9. the method for a kind of starch according to claim 1, cellulose solids powder surface hydroxyl modification, it is characterized in that, when starch or cellulose solids powder being invested in homogenizer together with catalyzer, described catalyst content is the 0.5-8% of starch or cellulose solids powder and total catalyst weight.
10. the method for a kind of starch according to claim 1, cellulose solids powder surface hydroxyl modification, it is characterized in that, when starch or cellulose solids powder, catalyzer, polyolefine being invested in homogenizer together with processing aid, described catalyst content is the 0.5-8% of starch or cellulose solids powder, catalyzer, polyolefine and processing aid gross weight.
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| CN110903580A (en) * | 2019-11-27 | 2020-03-24 | 桂林理工大学 | Silicomolybdic acid compatibilization modified polyvinyl alcohol/starch composite material and preparation method thereof |
| CN110964339A (en) * | 2019-12-24 | 2020-04-07 | 黑龙江幸福人生态农业开发股份有限公司 | Preparation method of bio-based composite material film with good air tightness |
| CN111647258A (en) * | 2020-06-09 | 2020-09-11 | 绍兴诺鼎卫浴洁具股份有限公司 | Polystyrene modified polylactic acid composite material and preparation method thereof |
| CN112142987A (en) * | 2020-10-15 | 2020-12-29 | 中国科学院长春应用化学研究所 | Modified starch, preparation method thereof, starch film and preparation method thereof |
| CN113150435A (en) * | 2021-03-31 | 2021-07-23 | 东燊新材料科技(深圳)有限公司 | High-temperature-resistant degradable plastic material and preparation method thereof |
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| CN110903580A (en) * | 2019-11-27 | 2020-03-24 | 桂林理工大学 | Silicomolybdic acid compatibilization modified polyvinyl alcohol/starch composite material and preparation method thereof |
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