CN102702655B - Polyvinyl alcohol/high amylose biodegradable material and melting preparation method thereof - Google Patents

Polyvinyl alcohol/high amylose biodegradable material and melting preparation method thereof Download PDF

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Publication number
CN102702655B
CN102702655B CN201210192994.2A CN201210192994A CN102702655B CN 102702655 B CN102702655 B CN 102702655B CN 201210192994 A CN201210192994 A CN 201210192994A CN 102702655 B CN102702655 B CN 102702655B
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China
Prior art keywords
high amylose
polyvinyl alcohol
amylose starch
stabilizer
thermo
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Expired - Fee Related
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CN201210192994.2A
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Chinese (zh)
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CN102702655A (en
Inventor
徐卫兵
王雷
陈俊伟
周正发
汪瑾
任凤梅
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Hefei University of Technology
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Hefei University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • B29C2948/9259Angular velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885Screw or gear
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing

Abstract

The invention discloses a polyvinyl alcohol/high amylose biodegradable material and a melting preparation method thereof. The method comprises the following steps: uniformly mixing polyvinyl alcohol, high amylase, heat stabilizer, inorganic filler, low molecular weight plasticizer and processing assistant agent in a high-speed mixer at the temperature of 70 to 120 DEG C; and then, melting, extruding and pelleting the mixture in a double-screw extruder, wherein the temperature of a charging barrel is 130 to 190 DEG C. By the method, a composite system of the low molecular weight plasticizer is rationally selected and a proper amount of processing assistant agent and heat stabilizer are added to successfully implement the thermoplastic molding of the polyvinyl alcohol/high amylose, therefore, not only the melting processing problem of the polyvinyl alcohol/high amylase is solved, but also the processability, mechanical property and biodegradability of the composite material are improved.

Description

A kind of polyvinyl alcohol/high amylose starch biological degradable composite material and fusion preparation method thereof
One, technical field
The present invention is a kind of preparation field of biological degradable composite material, specifically a kind of fusion preparation method of polyvinyl alcohol/high amylose starch biological degradable composite material.
Two, background technology
Along with the development of plastics industry, the exploitation of plastics variety, more and more plastics become people survive in indispensable material.Traditional plastics are difficult to biological degradation, a large amount of heaps of plastic refuse the seriously polluted of environment of being rivals in a contest.In addition, plastics are to make by petroleum path mostly, and oil is nonrenewable resource, and in current oil shortage, expensive situation, the development of plastics will be subject to serious impact.Under such background, research bio-degradable plastics, the meaning of developing renewable resources is very great.
Polyvinyl alcohol is a kind of biodegradable high molecular polymer, has the advantages such as high barrier, static resistance, wear resistant corrosion resistant, good mechanical performance.Starch can be processed extraction from farm crop, various in style, is a kind of natural reproducible resource, fully biodegradable.
In current biodegradable material, mainly take macromolecular materials such as starch, poly(lactic acid), poly butylene succinate, polyoxyethylene glycol, polyacrylate(s)s as main.CN102140234A discloses the preparation method take poly(lactic acid) and poly butylene succinate as main biodegradable composite, but though the biodegradability of poly(lactic acid) is good, its price is higher, and mechanical property is undesirable.CN102140234A is disclosed a kind of by polydactyl acid and the compound preparation method who adds again the inorganic filler composite materials such as calcium carbonate of poly butylene succinate, wherein poly butylene succinate is fermented and is made by Biological resources, the source of raw material is harsher like this, is difficult to meet the demand in market.CN102226014A discloses the preparation method of a kind of starch and poly butylene succinate biodegradable material, but the mechanical property of starch is poor, still needs to improve.
Three, summary of the invention
The present invention aims to provide a kind of polyvinyl alcohol/high amylose starch biological degradable composite material and fusion preparation method thereof, and technical problem to be solved is to make matrix material in possessing biological degradability, improve its mechanical property.
The present invention, take polyvinyl alcohol as main raw material, adds appropriate high amylose starch blending and modifying, and high amylose starch and polyvinyl alcohol have good consistency, and high amylose starch can make the plasticity of polyvinyl alcohol strengthen, and improves the processing characteristics of matrix material.In addition high amylose starch add the biodegradability large increase that makes matrix material.Prepare polyvinyl alcohol/high amylose starch Biodegradable material by efficient compound speedup system and processing aid, appropriate thermo-stabilizer and mineral filler melting.Matrix material of the present invention has good biodegradability and mechanical property, and preparation technology is simple, and raw material sources are abundant.
Polyvinyl alcohol/high amylose starch biological degradable composite material of the present invention, is characterized in that its raw material is configured to by mass fraction:
Component A:PVA60-90 part, high amylose starch 10-40 part, thermo-stabilizer 0.2-3 part, mineral filler 0.5-5 part;
Component B: small molecules composite elasticizer, addition is the 10-40% of component A total mass;
Processing aid, addition is the 0.2-2% of component A total mass;
Described processing aid is selected from PE wax or whiteruss.
The polymerization degree of described PVA is 1700, and alcoholysis degree is 88%.
Described high amylose starch is the starch of amylose starch quality percentage composition at 30-80%.
Described thermo-stabilizer is selected from Zinic stearas and/or calcium stearate, if ratio is any when several.
Described mineral filler is nano silicon or modified montmorillonoid.
Described small molecules softening agent is any two or three in diethanolamine, otan, diglycerol, if ratio is any when several.
Polyvinyl alcohol/high amylose starch biological degradable composite material of the present invention, comprises batch mixing and extruding pelletization process, it is characterized in that:
Described batch mixing is that PVA, high amylose starch, thermo-stabilizer and mineral filler are mixed to obtain to compound a in 70-100 ℃, then adds small molecules composite elasticizer and processing aid to mix in 70-120 ℃, is cooled to room temperature and obtains compound b;
Described extruding pelletization is by described compound b extruding pelletization in twin screw extruder, and barrel temperature is 130-190 ℃, screw speed 200-250 rev/min.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention is take polyvinyl alcohol as main, and high amylose starch is auxiliary, can effectively improve mechanical property, barrier property, the wear resisting property of matrix material, makes again matrix material have good processing characteristics and biodegradability.High amylose starch has better thermostability, mechanical property, biodegradability than traditional starch, and amylose crystallization degree is lower, and fusing point is lower.
2, the present invention, mainly with environment-protecting asepsis, efficient small molecules softening agent compound use, makes plasticization effect obvious.
3, the present invention uses appropriate thermo-stabilizer, has added appropriate processing aid, changes polyvinyl alcohol/high amylose starch biological degradable composite material at processing characteristics, effectively reduces the decomposition of matrix material work in-process.
3, the present invention uses appropriate nanometer inorganic filler, has effectively improved the mechanical property of matrix material.
Four, accompanying drawing explanation
Fig. 1 is the thermogravimetric curve (TG) of matrix material of the present invention.Wherein curve a is matrix material prepared by embodiment 1, curve b is matrix material prepared by embodiment 2, curve c is matrix material prepared by embodiment 3, and curve d is matrix material prepared by embodiment 4, and curve e is that the formula of embodiment 2 matrix materials removes the matrix material of preparing after thermo-stabilizer.
As can be seen from the figure, after adding the thermo-stabilizer of 0.5 part of left and right, matrix material improves a lot than the thermostability that does not add any thermo-stabilizer, thermogravimetric curve is to elevated temperature excursions, the more thermostabilitys of thermo-stabilizer consumption are relatively better, and in the time of Zinic stearas and calcium stearate compound use, compare Heat stability is good while use separately.
Five, embodiment
Be some examples described in the invention below, just to aid illustration of the present invention, still belong to protection domain if there are personnel that foregoing invention is made nonessential modification or adjusted.
In example, PVA1788 used is that Anhui Province reform material stock company produces below; High amylose starch: Agricultural University Of Anhui cultivates; Diethanolamine: Chemical Reagent Co., Ltd., Sinopharm Group; Otan: Wuhan Yuancheng Technology Development Co., Ltd.; Diglycerol: Chemical Reagent Co., Ltd., Sinopharm Group; Whiteruss: Chemical Reagent Co., Ltd., Sinopharm Group; PE wax: Shanghai Xin Nuo Chemical Co., Ltd.; Zinic stearas: Xin Wangsu industry company limited of Liyang City; Calcium stearate: Xin Cheng Chemical Co., Ltd. of Foshan City; Modified montmorillonoid: GK-7, Jiangxi Gu Kang novel material company limited produces; Nano silicon: smart Ya Na meter novel material company limited converges in Shanghai.
Embodiment 1:
The PVA1788 of 85 parts and the high amylose starch of 15 parts, the Zinic stearas of 0.3 part, the calcium stearate of 0.3 part, the modified montmorillonoid of 1.5 parts are mixed 20 minutes in 70-100 ℃ in high-speed mixer, and then add 10 parts of otans, the diethanolamine of 20 parts and 0.5 part of whiteruss in high-speed mixer 70-85 ℃ mix 20 minutes, cool to room temperature is extruding pelletization in twin screw extruder, and barrel temperature is that 130-190 ℃, screw speed are 210 revs/min.
The tensile strength that records matrix material sample is 23.5MPa, and elongation at break is 350%, buries method to its degradation experiment with soil, and the cycle is 4 months, and the rate of weight loss of material is 37%.
Embodiment 2:
By the high amylose starch of the PVA1788 of 80 parts and 20 parts, 0.2 part of Zinic stearas, 0.2 calcium stearate, 1 part of nano silicon 70-100 ℃ of high-speed mixing 20 minutes in high-speed mixer, then add 10 parts of diglycerols and 20 parts of diethanolamine, 0.5 part of PE wax in high-speed mixer 70-85 ℃ mix 15 minutes.By compound extruding pelletization in twin screw extruder, barrel temperature is that 130-190 ℃, screw speed are 240 revs/min.
The front degree of stretching that records matrix material sample is 21.8MPa, and elongation is 380%.Bury method to its degradation experiment with soil, the cycle is 4 months, and the rate of weight loss of material is 43%.
Embodiment 3:
By the high amylose starch of the PVA1788 of 70 parts and 30 parts, the Zinic stearas of 0.4 part, 2 parts of modified montmorillonoids 70-100 ℃ of high-speed mixing 15 minutes in high-speed mixer, then add 20 parts of otans, the diethanolamine of 10 parts, 0.3 part of PE wax 90-110 ℃ of high-speed mixing 15 minutes in high-speed mixer, cool to room temperature is extruding pelletization in twin screw extruder, barrel temperature is 130-190 ℃, and screw speed is 220 revs/min.
The tensile strength that records matrix material sample is 17.9MPa, and elongation is 410%.Bury method to its degradation experiment with soil, the cycle is 4 months, and the rate of weight loss of material is 53%.
Embodiment 4:
By 60 parts of PVA1788 and 40 portions of high amylose starchs, 0.5 part of Zinic stearas, 1.5 parts of nano silicons 95 ℃ of high-speed mixing 15 minutes in high-speed mixer, then add the otan of 15 parts, 10 parts of diethanolamine, 5 parts of diglycerols and 1 part of whiteruss in high-speed mixer 70-115 ℃ mix 20 minutes, then extruding pelletization in bolt screw extrusion press, barrel temperature 130-190 ℃, screw speed is 215 revs/min.
The tensile strength that records matrix material sample is 16.5MPa, and elongation is 449%.Bury method to its degradation experiment with soil, the cycle is 4 months, and the rate of weight loss of material is 61%.
Table 1 is the mechanical experimental results of each embodiment matrix material, and as seen from table, matrix material has good mechanical strength and elongation, and composite material toughness is better.In addition, matrix material is along with the relative increase of starch consumption, and the tensile strength of material declines to some extent, and elongation increases, and toughness increases.
The data of mechanical of table 1 matrix material

Claims (1)

1. polyvinyl alcohol/high amylose starch biological degradable composite material, is characterized in that its raw material is configured to by mass fraction:
Component A:PVA 60-90 part, high amylose starch 10-40 part, thermo-stabilizer 0.2-3 part, mineral filler 0.5-5 part;
Component B: small molecules composite elasticizer, addition is the 10-40% of component A total mass;
Processing aid, addition is the 0.2-2% of component A total mass;
Described processing aid is selected from PE wax or whiteruss;
The polymerization degree of described PVA is 1700, and alcoholysis degree is 88%;
Described high amylose starch is the starch of amylose starch quality percentage composition at 30-80%;
Described thermo-stabilizer is selected from Zinic stearas and/or calcium stearate;
Described mineral filler is nano silicon or modified montmorillonoid;
Described small molecules softening agent is any two or three in diethanolamine, otan, diglycerol;
Described polyvinyl alcohol/high amylose starch biological degradable composite material is the matrix material preparing by the following method:
PVA, high amylose starch, thermo-stabilizer and mineral filler are mixed to obtain to compound a in 70-100 ℃, then add small molecules composite elasticizer and processing aid to mix in 70-120 ℃, be cooled to room temperature and obtain compound b; By described compound b extruding pelletization in twin screw extruder, barrel temperature is 130-190 ℃, screw speed 200-250 rev/min.
CN201210192994.2A 2012-06-12 2012-06-12 Polyvinyl alcohol/high amylose biodegradable material and melting preparation method thereof Expired - Fee Related CN102702655B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108676299A (en) * 2018-05-23 2018-10-19 安徽新华学院 A kind of complete biodegradable plastic and its production technology
CN109181012A (en) * 2018-08-15 2019-01-11 李泽 Plant amylum Biodegradable Materials

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1066077A (en) * 1991-03-19 1992-11-11 帕克戴维斯公司 Biodegradable amyloid composition
CN101360783A (en) * 2004-10-18 2009-02-04 普朗蒂克科技有限公司 Barrier film
CN101397081A (en) * 2007-09-30 2009-04-01 江门市宝德利水溶性塑料有限公司 Toilet-flushing type biodegradable collection bag

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1066077A (en) * 1991-03-19 1992-11-11 帕克戴维斯公司 Biodegradable amyloid composition
CN101360783A (en) * 2004-10-18 2009-02-04 普朗蒂克科技有限公司 Barrier film
CN101397081A (en) * 2007-09-30 2009-04-01 江门市宝德利水溶性塑料有限公司 Toilet-flushing type biodegradable collection bag

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
高直链玉米淀粉-PVA共混塑料薄膜的制作工艺的研究;黄晓杰 等;《食品工业科技》;20061231;第27卷(第3期);第160-161 *
黄晓杰 等.高直链玉米淀粉-PVA共混塑料薄膜的制作工艺的研究.《食品工业科技》.2006,第27卷(第3期),160-161.

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