CN105001569B - A kind of polyvinyl alcohol/oyster shell whiting biomass composite and preparation method thereof - Google Patents
A kind of polyvinyl alcohol/oyster shell whiting biomass composite and preparation method thereof Download PDFInfo
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- CN105001569B CN105001569B CN201510392452.3A CN201510392452A CN105001569B CN 105001569 B CN105001569 B CN 105001569B CN 201510392452 A CN201510392452 A CN 201510392452A CN 105001569 B CN105001569 B CN 105001569B
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 87
- 241000276489 Merlangius merlangus Species 0.000 title claims abstract description 75
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 67
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 239000002028 Biomass Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 239000004014 plasticizer Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 238000006136 alcoholysis reaction Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- -1 propionyl Amine Chemical class 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 4
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 150000008431 aliphatic amides Chemical class 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 229940043237 diethanolamine Drugs 0.000 claims description 4
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- QBUKAFSEUHGMMX-MTJSOVHGSA-N (5z)-5-[[3-(1-hydroxyethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical compound C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1C(C)O QBUKAFSEUHGMMX-MTJSOVHGSA-N 0.000 abstract 1
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 2
- 229940080818 propionamide Drugs 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 235000015170 shellfish Nutrition 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 102000003886 Glycoproteins Human genes 0.000 description 1
- 108090000288 Glycoproteins Proteins 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001483 mobilizing effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010420 shell particle Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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Landscapes
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of polyvinyl alcohol/oyster shell whiting biomass composite disclosed by the invention is made up of following components through melt blending by weight：The fusing point of 20 80 parts of polyvinyl alcohol, 20 80 parts of oyster shell whiting, 10 30 parts of plasticizer, and the composite is 155~200 DEG C, and heat decomposition temperature is 230~270 DEG C, and tensile strength is 30~80MPa, and elongation at break is 80~300%.Invention additionally discloses its preparation method.Because polyvinyl alcohol selected in composite of the present invention and polarity oyster shell whiting have good natural compatibility, it is dispersed in polyvinyl alcohol matrix to realize oyster shell whiting to additionally use pan type physico chemical reactor in addition, thus can be in the case of without surface modifier and flow ability modifying agent, not only considerably increase oyster shell whiting loading, and also improve the mechanical property and elongation at break of composite, while preparation method process is simple, flow is short, production process three-waste free pollution, it is easy to accomplish industrialization production.
Description
Technical field
The invention belongs to polymer/biomass composite and its preparing technical field, and in particular to a kind of melting adds
The polyvinyl alcohol of work/oyster shell whiting biomass composite and preparation method thereof.
Background technology
Under current crisis of the increasingly serious shortage of resources with environmental pollution, renewable resource is made full use of, develop ring
Border friendly materials, the critical task that reduction pollution, environmental protection have faced as the national economic development.Natural seashell is by software
Long term Animal mineralization is formed, and belongs to typical organic/inorganic hybridization material, is important bio-renewables.In recent years
Come, as China's shellfishery is developed rapidly, a large amount of waste shells of generation form many " shell mountains " in coastal area, this
The bio-renewables of preciousness are not only wasted, also serious burden is caused to environment.Therefore, realize to waste shell resource
Change, higher value application turns into problem demanding prompt solution, is also a significant challenge.
95% is calcium carbonate (CaCO in shell3), 5% is organic matter, is by calcite (CaCO3, trigonal system) or aragonite
(CaCO3, orthorhombic system) lamella and organic matter such as protein, glycoprotein, phosphatide and polysaccharide etc. intersect it is laminated pile up formed
A kind of organic/inorganic laminar composite, its hardness and toughness respectively may be about 10 times and 1000 times of ordinary calcium carbonate.Therefore,
To be expected to be used as enhancing by polymer filler instead of calcium carbonate after shell pulverization process, this can not only realize bio-renewables
Make full use of, turn waste into wealth, while can also reduce ore resource consumption and environmental pollution etc..Wang Wei is reported and is used silane coupler
With titanate coupling agent modified oyster shell whiting enhancing polyethylene (Wang Wei, Chen Ying, tie up the people by the emperor himself, Donghua University's journal (natural science edition),
2011,06)；It is raw material that Li Haiyan is reported with discarded mussel shell, after removing cuticula, crushings, grinding, emulsification pretreatment with gather
Propylene blending prepare composite (Li H, Tan Y, Zhang L, Journal of Hazardous Materials, 2012,
217)；Jiang Xuewen report by silane coupler process oyster shell whiting prepare free volume properties in epoxy resin/shell particles composites (Jiang Xuewen,
Bright red flag, Ji Genzhong, etc. engineering plastics application, 2007,08)；CN 102827406 discloses a kind of using at rare-earth coupling agent
Oyster shell whiting filling epoxidized natural rubber composite material of reason and preparation method thereof；CN 101633775 it is open using coupling agent or
Isocyanates is surface-treated sea shell micropowder, for filling polylactic acid, polyhydroxyalkanoate or poly butylene succinate etc.；Liu
Gloomy the reporting in source prepares nylon 6 composite material (Liu Yuansen, Zhang Cong by the modified oyster shell powder filling of organic silicon surfactant
It is beautiful, Cheng Yanbo, etc., polymer material science and engineering, 2015,02).But polymer/shellfish prepared by current the above method
Shell powder composite material still suffers from problems with：
(1) because polymeric matrix used is generally the non-polar polymers such as polyethylene, polypropylene, natural rubber, thus it is
Improve the compatibility of polar filler oyster shell whiting and polymer, just oyster shell whiting surface must be chemically treated, this will lead
Complex process is caused, production efficiency is low；
(2) because traditional polymer melting extrusion processing mode is difficult to filling oyster shell whiting high in polymeric matrix
It is dispersed, the mechanical property of high content shell powder composite material can be undoubtedly reduced, so that the use of the material can be limited, in order to
Influence of the oyster shell whiting to composite materials property is reduced, the loading of usual this oyster shell whiting is below 25wt%, not only makes
The recycling of shell is limited, and the cost reduction of material is also limited.
(3) because the matrix resins such as polyethylene used, polypropylene are difficult to degrade under field conditions (factors), thus can bring secondary
Pollution.
The content of the invention
It is an object of the invention to be directed to the problem that existing shell recycling is present, there is provided it is a kind of it is environment-friendly, into
This cheap, high mechanical strength, biodegradable polyvinyl alcohol/oyster shell whiting biomass composite.
It is a further object of the present invention to provide a kind of side for preparing above-mentioned polyvinyl alcohol/oyster shell whiting biomass composite
Method.
Polyvinyl alcohol/oyster shell whiting biomass composite that the present invention is provided, it is characterised in that the composite is by weight
Part meter is made up of following components through melt blending：
Polyvinyl alcohol 20-80 parts
Oyster shell whiting 20-80 parts
Plasticizer 10-30 parts,
Wherein the degree of polymerization of polyvinyl alcohol is 300~2400, and alcoholysis degree is 80~99%, and the average grain diameter of oyster shell whiting is
0.1~100 μm, plasticizer is mass ratio 20~70:At least one composition in 30~80 water and non-aqueous plasticizer, and this is multiple
The fusing point of condensation material is 155~200 DEG C, and heat decomposition temperature is 230~270 DEG C, and tensile strength is 30~80MPa, extension at break
Rate is 80~300%.
Non-aqueous plasticizer is polyalcohol, aliphatic amide, aliphatic hydramine and the poly- second of low-molecular-weight in above composite
Glycol, wherein it is preferred that ethylene glycol, glycerine, BDO, neopentyl glycol, pentaerythrite, acetamide, propionamide, urea, oneself
Lactams, monoethanolamine, diethanol amine, diglycolamine, Propanolamine and number-average molecular weight are 200~6000 polyethylene glycol.
The degree of polymerization of polyvinyl alcohol preferably 500~1700 in above composite, alcoholysis degree preferably 92~99%.
Oyster shell whiting is the powder that discarded sea shells and cultivation shell are crushed in above composite, and average grain diameter is preferred
0.5~50 μm；
The preparation method of polyvinyl alcohol/oyster shell whiting biomass composite that the present invention is provided, it is characterised in that the method
Processing step and condition it is as follows：
(1) after first shell washing is dried, average grain diameter is crushed to for 0.01~10mm, then will crush the shell for obtaining
In powder 20-80 parts and polyvinyl alcohol 20-80 parts addition pan type physico chemical reactor, cut in solid phase under 50~300r/min of rotating speed
Cut and be pulverized and mixed 1~40 time, obtain polyvinyl alcohol/oyster shell whiting biomass mixing that oyster shell whiting average grain diameter is 0.1~100 μm
Material；
(2) by gained compound and 10~30 parts of addition high-speed mixers of plasticizer, in 50-80 DEG C of temperature with rotating speed
300~800r/min mixes 3~6h；
(3) in the mixture addition screw extruder for preparing step (2), in 60~200r/min of rotating speed, extrusion temperature
Melting extrusion, granulation, that is, be obtained the polyvinyl alcohol/shell powder composite material of melt-processable at 170~210 DEG C；
The number of above material is weight portion, wherein the degree of polymerization of the polyvinyl alcohol is 300~2400, alcoholysis degree is
80~99%；Plasticizer is mass ratio 20~70:At least one composition in 30~80 water and non-aqueous plasticizer.
Non-aqueous plasticizer described in above method is polyalcohol, aliphatic amide, aliphatic hydramine and the poly- second of low-molecular-weight
Glycol, the specific preferred ethylene glycol of polyalcohol, glycerine, BDO, neopentyl glycol, pentaerythrite；Aliphatic amide is preferred
Acetamide, propionamide, urea, caprolactam；Aliphatic hydramine preferred alcohol amine, diethanol amine, diglycolamine, Propanolamine；It is low
Molecular weight polyethylene glycol is selected from the polyethylene glycol that number-average molecular weight is 200~6000.
Shell described in above method is discarded sea shells and cultivation shell；After shell washing drying, preferably it is crushed to
Average grain diameter is 0.1~5mm.
The degree of polymerization of polyvinyl alcohol described in above method preferably 500~1700；Alcoholysis degree preferably 92~99%.
Mixing oxides solid method mixes preferably 5~35 times in above method.
Pan type physico chemical reactor described in above method is the force-chemical reaction disclosed in ZL 95 1 11258.9
Device.
Above method gained composite can further by routine thermoplastic processing method be prepared into fiber, strand, film,
The products such as sheet material, sheet material, hollow container, Injection moulded part, can be used for reinforcing material, packaging material, material for water treatment, obstruct material
The fields such as material, writing paper, wallpaper, toy and 3D printing.
The present invention compared with prior art, with advantages below：
(1) because the polymer that the present invention is selected is polyvinyl alcohol, it is not only biodegradable macromolecular material, and
The characteristics of also there is polyhydroxy strong hydrogen bonding, thus it has good natural compatibility with polarity oyster shell whiting, can both not add
Plus high-performance, low cost, environment-friendly polyvinyl alcohol based composites are prepared in the case of surface modifier, shellfish can be increased again
Shell powder loading, improves the resource utilization rate of shell.
(2) because the present invention carries out melt blending from polyvinyl alcohol and oyster shell whiting, thus using having in oyster shell whiting
There is interaction of hydrogen bond in machine matter, the intramolecular and intermolecular hydrogen bonding of partial destruction polyvinyl alcohol itself are played with polyvinyl alcohol
Collaboration plasticization, (such as the A's of publication number CN 102643497 is special with existing inorganic powder filled polyvinyl alcohol composite material
Profit) compare, in the case of identical inorganic filler content, the polyvinyl alcohol based composites prepared by the present invention have more preferable
Thermoplastic processability, both avoids the mechanical property for adding flow ability modifying agent to influence composite, and processing cost is reduced again.
(3) because the inventive method is using the unique crushing of pan type physico chemical reactor, dispersion, mixing and power chemistry
Mobilizing function is dispersed in polyvinyl alcohol matrix to realize oyster shell whiting, thus substantially increases the mechanics of composite
Performance and elongation at break.
(4) fluoropolymer resin contained in the composite provided due to the present invention is polyvinyl alcohol, under certain condition
Biodegradable, contained oyster shell whiting is bio-renewables, and contained plasticizer is also environment-friendly, cleans what is be easy to get
Compound, thus make the polyvinyl alcohol/oyster shell whiting biomass composite of acquisition for a kind of environment friendly material, will not be to ring
Border forms secondary pollution.
(5) preparation method of the polyvinyl alcohol/oyster shell whiting biomass composite provided due to the present invention, process is simple,
Flow is short, production process three-waste free pollution, thus is easily achieved industrialization production.
(6) due to polyvinyl alcohol/oyster shell whiting biomass composite that the present invention is provided have it is good can thermoplastic processing
Performance, excellent mechanical property, and it is biodegradable under certain bar, further can be prepared by conventional thermoplastic processing method fine
The products such as dimension, strand, film, sheet material, sheet material, hollow container, injection-molded item, for reinforcing material, packaging material, water process material
The fields such as material, barrier material, writing paper, wallpaper, toy and 3D printing, thus polyvinyl alcohol application field can have both been widened, again may be used
Realize the environment-friendly recycling of waste shell.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be that following examples are served only for
The present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations can be made according to the invention described above.
What deserves to be explained is：1) number of following examples material is parts by weight；2) gained is multiple in following examples
The fusing point of condensation material is tested using U.S.'s TA companies Q20 types differential scanning calorimeter (DSC)：By the composite of 6mg or so
Sample is placed in crucible and seals, test temperature：Room temperature~250 DEG C, heating rate：10 DEG C/min, nitrogen atmosphere, flow velocity：50mL/
min；3) decomposition temperature of gained composite is tested using U.S.'s TA companies Q50 types thermogravimetric analyzer in following examples,
Test temperature：Room temperature~600 DEG C；Heating rate：10℃/min；Nitrogen atmosphere；Flow velocity：50mL/min；4) following examples institute
The tensile strength for obtaining composite is according to GB/T 1040-2006, using the M4010 of Shenzhen Rui Geer Instrument Ltd.
Type microcomputer controlled electronic universal tester is tested.Draw speed：50mm/min, parameter value is averaged by five samples and obtained.
Embodiment 1
First by 50 parts of washings dry it is size-reduced to average grain diameter for the oyster shell whiting and 50 parts of degree of polymerization of 0.1mm are 2400, alcohol
Xie Du be 88% polyvinyl alcohol add pan type physico chemical reactor in, mix in mixing oxides solid method under rotating speed 220r/min
35 times, obtain polyvinyl alcohol/oyster shell whiting biomass compound that oyster shell whiting average grain diameter is 0.1 μm；By gained compound and 15
Part is by mass ratio 50:40:The plasticizer of 10 water, pentaerythrite and acetamide composition is added in high-speed mixer, 55
DEG C, rotating speed 500r/min mixing 5h；By gained mixture add double screw extruder in, in rotating speed 100r/min, extrusion temperature
Melting extrusion, granulation, that is, be obtained the polyvinyl alcohol/oyster shell whiting biomass composite of melt-processable at 205 DEG C.
The fusing point of the composite is 191 DEG C, and heat decomposition temperature is 259 DEG C, and tensile strength is 56MPa, elongation at break
It is 156%.
Embodiment 2
First by 70 parts of washings dry it is size-reduced to the oyster shell whiting of average grain diameter 3.1mm and 30 parts of degree of polymerization be 1700, alcoholysis
The polyvinyl alcohol spent for 99% is added in pan type physico chemical reactor, in mixing oxides solid method mixing 20 under rotating speed 155r/min
It is secondary, obtain polyvinyl alcohol/oyster shell whiting biomass compound that oyster shell whiting average grain diameter is 7.1 μm；By gained compound and 18 parts
By mass ratio 30:20:The plasticizer of 50 water, glycerine and monoethanolamine composition is added in high-speed mixer, in 70 DEG C, turns
Fast 700r/min mixing 4h；By gained mixture add double screw extruder in, in rotating speed 150r/min, 195 DEG C of extrusion temperature
Lower melting extrusion, granulation, that is, be obtained the polyvinyl alcohol/oyster shell whiting biomass composite of melt-processable.
The fusing point of the composite is 172 DEG C, and heat decomposition temperature is 262 DEG C, and tensile strength is 80MPa, elongation at break
It is 91%.
Embodiment 3
First by 55 parts of washings dry it is size-reduced to the oyster shell whiting of average grain diameter 7.8mm and 45 parts of degree of polymerization be 2000, alcoholysis
The polyvinyl alcohol spent for 99% is added in pan type physico chemical reactor, in mixing oxides solid method mixing 30 under rotating speed 200r/min
It is secondary, obtain polyvinyl alcohol/oyster shell whiting biomass compound that oyster shell whiting average grain diameter is 86 μm；By gained compound and 22 parts by
Mass ratio 55:20:The plasticizer of 25 water, urea and polyethylene glycol composition that number-average molecular weight is 2000 adds mixed at a high speed
In conjunction machine, in 60 DEG C, rotating speed 600r/min mixing 4.5h；By gained mixture add single screw extrusion machine in, in rotating speed 160r/
Min, melting extrusion, granulation at 183 DEG C of extrusion temperature, that is, polyvinyl alcohol/oyster shell whiting that melt-processable is obtained is biomass combined
Material.
The fusing point of the composite is 164 DEG C, and heat decomposition temperature is 248 DEG C, and tensile strength is 49MPa, elongation at break
It is 145%.
Embodiment 4
First by 20 parts of washings dry it is size-reduced to average grain diameter for the oyster shell whiting and 80 parts of degree of polymerization of 0.01mm are 300, alcohol
Xie Du be 80% polyvinyl alcohol add pan type physico chemical reactor in, under rotating speed 50r/min mixing oxides solid method mixing 1
It is secondary, obtain polyvinyl alcohol/oyster shell whiting biomass compound that oyster shell whiting average grain diameter is 8.5 μm；By gained compound and 25 parts
By mass ratio 70:The plasticizer of 30 water and diglycolamine composition is added in high-speed mixer, in 50 DEG C, rotating speed 300r/
Min mixing 6h；By in gained mixture addition double screw extruder, melted at rotating speed 200r/min, 170 DEG C of extrusion temperature and squeezed
Go out, granulate, that is, the polyvinyl alcohol/oyster shell whiting biomass composite of melt-processable is obtained.
The fusing point of the composite is 155 DEG C, and heat decomposition temperature is 230 DEG C, and tensile strength is 36.3MPa, extension at break
Rate is 300%.
Embodiment 5
First by 60 parts of washings dry it is size-reduced to average grain diameter for the oyster shell whiting and 40 parts of degree of polymerization of 0.4mm are 1000, alcohol
Xie Du be 95% polyvinyl alcohol add pan type physico chemical reactor in, mix in mixing oxides solid method under rotating speed 100r/min
25 times, obtain polyvinyl alcohol/oyster shell whiting biomass compound that oyster shell whiting average grain diameter is 0.5 μm；By gained compound and 20
Part is by mass ratio 60:10:The plasticizer of 30 water, diethanol amine and polyethylene glycol composition that number-average molecular weight is 6000 adds
In entering high-speed mixer, in 60 DEG C, rotating speed 600r/min mixing 4.5h；By gained mixture add single screw extrusion machine in,
Rotating speed 80r/min, melting extrusion, granulation at 190 DEG C of extrusion temperature are obtained the polyvinyl alcohol/oyster shell whiting life of melt-processable
Substance composite.
The fusing point of the composite is 169 DEG C, and heat decomposition temperature is 254 DEG C, and tensile strength is 67MPa, elongation at break
It is 124%.
Embodiment 6
First by 30 parts of washings dry it is size-reduced to average grain diameter for the oyster shell whiting and 70 parts of degree of polymerization of 10mm are 500, alcoholysis
The polyvinyl alcohol spent for 92% is added in pan type physico chemical reactor, in mixing oxides solid method mixing 40 under rotating speed 300r/min
It is secondary, obtain polyvinyl alcohol/oyster shell whiting biomass compound that oyster shell whiting average grain diameter is 50 μm；By gained compound and 18 parts by
Mass ratio 20:40:The plasticizer of 40 water, BDO and caprolactam composition is added in high-speed mixer, 80
DEG C, rotating speed 800r/min mixing 3h；By gained mixture add double screw extruder in, in rotating speed 180r/min, extrusion temperature
Melting extrusion, granulation, that is, be obtained the polyvinyl alcohol/oyster shell whiting biomass composite of melt-processable at 176 DEG C.
The fusing point of the composite is 158 DEG C, and heat decomposition temperature is 237 DEG C, and tensile strength is 42.3MPa, extension at break
Rate is 240%.
Embodiment 7
First by 80 parts of washings dry it is size-reduced to the oyster shell whiting of average grain diameter 1.2mm and 20 parts of degree of polymerization be 1700, alcoholysis
The polyvinyl alcohol spent for 99% is added in pan type physico chemical reactor, in mixing oxides solid method mixing 15 under rotating speed 180r/min
It is secondary, obtain polyvinyl alcohol/oyster shell whiting biomass compound that oyster shell whiting average grain diameter is 14 μm；By gained compound and 10 parts by
Mass ratio 40:20:The plasticizer of 40 water, neopentyl glycol and Propanolamine composition is added in high-speed mixer, in 75 DEG C, turns
Fast 800r/min mixing 3.5h；By gained mixture add double screw extruder in, in rotating speed 120r/min, extrusion temperature 210
Melting extrusion, granulation, that is, be obtained the polyvinyl alcohol/oyster shell whiting biomass composite of melt-processable at DEG C.
The fusing point of the composite is 200 DEG C, and heat decomposition temperature is 270 DEG C, and tensile strength is 62MPa, elongation at break
It is 80%.
Embodiment 8
First by 40 parts of washings dry it is size-reduced to average grain diameter for the oyster shell whiting and 60 parts of degree of polymerization of 5mm are 1700, alcoholysis
The polyvinyl alcohol spent for 97% is added in pan type physico chemical reactor, in mixing oxides solid method mixing 5 under rotating speed 260r/min
It is secondary, obtain polyvinyl alcohol/oyster shell whiting biomass compound that oyster shell whiting average grain diameter is 100 μm；By gained compound and 30 parts
By mass ratio 40:40:The plasticizer of 20 water, ethylene glycol and polyethylene glycol composition that number-average molecular weight is 200 adds high
In fast mixer, in 65 DEG C, rotating speed 400r/min mixing 5.5h；By gained mixture add single screw extrusion machine in, in rotating speed
60r/min, melting extrusion, granulation, that is, be obtained the polyvinyl alcohol/oyster shell whiting biomass of melt-processable at 177 DEG C of extrusion temperature
Composite.
The fusing point of the composite is 160 DEG C, and heat decomposition temperature is 243 DEG C, and tensile strength is 30MPa, elongation at break
It is 196%.
Claims (6)
1. a kind of preparation method of polyvinyl alcohol/oyster shell whiting biomass composite, it is characterised in that the processing step of the method
It is as follows with condition：
(1) after first shell washing is dried, average grain diameter is crushed to for 0.01~10mm, then will crush the oyster shell whiting for obtaining
In 20-80 parts and polyvinyl alcohol 20-80 parts addition pan type physico chemical reactor, in solid state shear under 50~300r/min of rotating speed
It is pulverized and mixed 1~40 time, obtains polyvinyl alcohol/oyster shell whiting biomass compound that oyster shell whiting average grain diameter is 0.1~100 μm；
(2) by gained compound and 10~30 parts of addition high-speed mixers of plasticizer, 50-80 DEG C of temperature with rotating speed 300~
800r/min mixes 3~6h；
(3) during the mixture for preparing step (2) adds screw extruder, in 60~200r/min of rotating speed, extrusion temperature 170~
Melting extrusion, granulation, that is, be obtained the polyvinyl alcohol/shell powder composite material of melt-processable at 210 DEG C；
The number of above material is weight portion, wherein the degree of polymerization of the polyvinyl alcohol be 300~2400, alcoholysis degree be 80~
99%；Plasticizer is mass ratio 20~70:At least one composition in 30~80 water and non-aqueous plasticizer；Obtained is fusible
The fusing point for melting the polyvinyl alcohol/shell powder composite material of processing is 155~200 DEG C, and heat decomposition temperature is 230~270 DEG C, stretching
Intensity is 30~80MPa, and elongation at break is 80~300%.
2. the preparation method of polyvinyl alcohol according to claim 1/oyster shell whiting biomass composite, it is characterised in that should
Non-aqueous plasticizer described in method is polyalcohol, aliphatic amide, aliphatic hydramine and low molecular poly.
3. the preparation method of polyvinyl alcohol according to claim 1/oyster shell whiting biomass composite, it is characterised in that should
Non-aqueous plasticizer described in method is ethylene glycol, glycerine, 1,4- butanediols, neopentyl glycol, pentaerythrite, acetamide, propionyl
Amine, urea, caprolactam, monoethanolamine, diethanol amine, diglycolamine, Propanolamine and number-average molecular weight are 200~6000 poly- second
Glycol.
4. the preparation method of the polyvinyl alcohol according to claim 1 or 2 or 3/oyster shell whiting biomass composite, its feature
The average grain diameter for being oyster shell whiting described in the method is 0.5~50 μm.
5. the preparation method of the polyvinyl alcohol according to claim 1 or 2 or 3/oyster shell whiting biomass composite, its feature
It is that mixing oxides solid method described in the method is mixed into 5~35 times.
6. the preparation method of polyvinyl alcohol according to claim 4/oyster shell whiting biomass composite, it is characterised in that should
Mixing oxides solid method described in method is mixed into 5~35 times.
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| CN105769798A (en) * | 2016-05-16 | 2016-07-20 | 张阳 | Preparation method of medicine for treating hypertension |
| CN109983074A (en) * | 2016-10-18 | 2019-07-05 | 株式会社可乐丽 | Purposes of the polyol as the plasticizer for polyvinyl alcohol in 3D printing method |
| CN107266724A (en) * | 2017-07-24 | 2017-10-20 | 陈登辉 | A kind of preparation method of hard hollow rubber material |
| CN111087723A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Polyvinyl alcohol composition with non-blocking film and good transparency, film, and preparation method and application thereof |
| CN110734616B (en) * | 2019-10-18 | 2022-02-15 | 安徽瑞鸿新材料科技有限公司 | Preparation method of polyvinyl alcohol-based composite material |
| CN111040439B (en) * | 2019-12-16 | 2022-04-01 | 浙江新力新材料股份有限公司 | Polyamide material with excellent wear resistance, and preparation method and application thereof |
| CN111234430B (en) * | 2019-12-17 | 2021-04-02 | 四川大学 | Polyvinyl alcohol-based composite powder for selective laser sintering and preparation method thereof |
| CN114773880B (en) * | 2022-04-24 | 2023-06-27 | 江西广源化工有限责任公司 | Superfine heavy calcium carbonate and preparation method thereof |
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