CN102634073A - Starch/polypropylene degradable composite material and preparation method thereof - Google Patents
Starch/polypropylene degradable composite material and preparation method thereof Download PDFInfo
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- CN102634073A CN102634073A CN2012101239345A CN201210123934A CN102634073A CN 102634073 A CN102634073 A CN 102634073A CN 2012101239345 A CN2012101239345 A CN 2012101239345A CN 201210123934 A CN201210123934 A CN 201210123934A CN 102634073 A CN102634073 A CN 102634073A
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- starch
- vestolen
- composite material
- degradable composite
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- 229920002472 Starch Polymers 0.000 title claims abstract description 170
- 235000019698 starch Nutrition 0.000 title claims abstract description 170
- 239000008107 starch Substances 0.000 title claims abstract description 170
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 21
- -1 polypropylene Polymers 0.000 claims abstract description 19
- 239000003921 oil Substances 0.000 claims description 35
- 235000019198 oils Nutrition 0.000 claims description 35
- 239000004902 Softening Agent Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 30
- 235000013311 vegetables Nutrition 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 13
- 238000005453 pelletization Methods 0.000 claims description 13
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical compound C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 claims description 5
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 244000017020 Ipomoea batatas Species 0.000 claims description 4
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 4
- 229920001592 potato starch Polymers 0.000 claims description 4
- 210000000582 semen Anatomy 0.000 claims description 4
- 235000019483 Peanut oil Nutrition 0.000 claims description 3
- 239000000312 peanut oil Substances 0.000 claims description 3
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 240000001085 Trapa natans Species 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 235000009165 saligot Nutrition 0.000 claims description 2
- 235000020238 sunflower seed Nutrition 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 abstract description 17
- 239000004033 plastic Substances 0.000 abstract description 17
- 239000004014 plasticizer Substances 0.000 abstract 2
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract 2
- 239000008158 vegetable oil Substances 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000001746 injection moulding Methods 0.000 description 33
- 239000005038 ethylene vinyl acetate Substances 0.000 description 22
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 22
- 239000003153 chemical reaction reagent Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 229920006238 degradable plastic Polymers 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 229940126680 traditional chinese medicines Drugs 0.000 description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 229920008262 Thermoplastic starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000010816 packaging waste Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004628 starch-based polymer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion 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
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means 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
- B29C48/40—Means 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a starch/polypropylene degradable composite material comprising the following raw materials in percentage by weight: 50% to 70% of starch, 5% to 15% of vegetable oil plasticizer, 15% to 30% of polypropylene or modified polypropylene and 5% to 30% of compatilizer. According to the composite material, the compatilizer is used for improving the compatibility of the starch and polypropylene, the vegetable oil plasticizer is used for plasticizing the starch, and the performance of the plasticized starch is stable, so that the toughness and impact resistance of the starch/polypropylene degradable composite material are enhanced greatly, the performance of the composite material is stable, and the composite material is applicable to the field of plastic package materials, farm-oriented mulching films, disposable tableware and the like. The invention also discloses a preparation method of the starch/polypropylene degradable composite material. The starch/polypropylene degradable composite material is simple to prepare, easy to implement, operate and control, low in preparation cost and apt to industrial production, thus having wide application prospect.
Description
Technical field
The present invention relates to the plastic material field, be specifically related to a kind of starch/Vestolen PP 7052 degradable composite material and preparation method thereof.
Background technology
Plastics industry develops rapidly, and its purposes has been penetrated into the every field of national economy, and purposes very extensively.The annual waste plastic that produces of China is about 5,000,000 tons, and wherein most of waste plastics are Vestolen PP 7052 (PP), Vilaterm (PE) and PS (PS) material, and these materials can not natural decomposition.Therefore; By the disposable plastic packaging waste of PP material, PE material, PS material prepn and corresponding agricultural film and disposable tableware, will be if arbitrarily abandoned because of its nondegradation is deposited on the soil, thus cause serious white pollution; And this potential pollutes simultaneously also increase and the accumulation of time that can the Along with people's usage quantity and aggravates; China's white pollution is serious at present, has caused the common concern of relevant government department and society, and relevant laws and regulations are put into effect; Especially in American-European market, the use of non-degradable plastics receives strict restriction.
Improving constantly of Along with people's environmental consciousness; Biodegradable environment-friendly material will receive increasing concern; The input of related industries chain and research and development forms; It is reported that the biodegradable demand of the U.S. will have 2,600,000,000 dollars the market space 2013, the demand of the present degradable plastics of China also is huge; According to the relevant industries analysis is 3,000,000 tons; Yet the degradable plastics of real meaning such as POLYACTIC ACID (PLA), polyhydroxyalkanoate (PHA) and poly butylene succinate prices such as (PBS) very costliness and performance have certain gap than conventional plastic such as PP and PE, cause its traction that in recent years, developed not high, and starch plastics (mainly be starch composite degradable plastics that the filling of PP, PE and PS or the like conventional plastic is obtained); Since its be with the basis of conventional plastic filling blend on grow up; The performance that not only has conventional plastic, and low price and have biodegradability, development at present are rapidly and enjoy the approval in industry member and market.
Though starch be can complete biodegradable natural high moleculer eompound owing to have notable difference with plastics on its structure, cause that consistency is poor between the two, thereby also limit its further application in this respect.At present, the method for improving plastics and starch consistency mainly comprises to the physically modified of starch and chemical modification, to the graft modification of plastics and add appropriate compatilizer.The introducing of compatilizer is that to use at present the most also be one of effective means.The compatilizer that the most often uses is multipolymer (EVA), Vestolen PP 7052/shrink glyceral methacrylate (PP/GMA) grafts and the starch/methyl acrylate graft copolymer etc. of ethylene-acrylic acid copolymer (EAA), ethene-vinyl acetate.The Chen Xian of Hunan University is grand to use shrink glyceral methacrylate (GMA) and the starch-grafted thing of the GMA/ compatilizer as Vestolen PP 7052/starch blending system in the presence of initiator; Use twin screw to extrude thermoplastification and starch and the polyacrylic blend increase-volume that has realized starch, prepared the biodegradable Vestolen PP 7052/starch blending material (the functional materials fifth phase in 2009 (40) volume) of excellent property.But this intermingling material does not add toughner, and intermingling material very difficult plasticizing in twin screw is extruded and can be highly brittle.
When solving starch and polypropylene compatible property, also need solve the too poor defective of toughness of whole compound system in addition; Because starch is rigid particles; General document all is it to be carried out plasticizing fill with patent report, and the method for employing is to add micromolecular compound such as polyvalent alcohol, polyamine, hydramine or the sweet acid esters of list and starch to carry out melt blending and plastify.Yu etc. use urea and ethanolamine mixtures as the softening agent for preparing thermoplastic starch, and in screw rod, carry out melt blending and extrude.After 15wt% urea and the composite use of 15wt% thanomin in the experiment discovery system, starch plasticizing back is with respect to using the glycerine plasticized starch to have better thermal property and mechanical property (Carbohydrate Polymers 64 (2006) 267-273).But adopt small molecules that starch is plastified, the plastifying starch performance is unstable, and small molecules is prone to separate out and causes the plasticized starch recrystallization to cause product performance to descend, and small molecules plastifying starch non-refractory, and product is prone to flavescence.Publication number is that the Chinese invention patent application of CN 101805463A discloses a kind of starch filled biodegradable polypropylene and preparation method thereof; This starch filled biodegradable polypropylene is by the starch of weight percent 30%～70%, 5%～15% softening agent, 10%～50% Vestolen PP 7052,0.5%～1% dispersion agent, 5%～8% toughner and 0.5%～1% photodegradable aid; Though the mechanical property of this starch filled biodegradable polypropylene is better; But the softening agent that is to use is one or both the mixture in sorbyl alcohol and the glycerine; Sorbyl alcohol and glycerine are the small molecules softening agent, still have above-mentioned problem.
Summary of the invention
The invention provides a kind of starch/Vestolen PP 7052 degradable composite material, starch and Vestolen PP 7052 are under the improvement of compatilizer and vegetables oil softening agent, and mechanical property is excellent, and anti-fold ability is strong, and the vegetables oil softening agent is difficult for separating out.
A kind of starch/Vestolen PP 7052 degradable composite material, process by the raw material of following weight percentage:
Starch 50%～70%;
Vegetables oil softening agent 5%～15%;
Vestolen PP 7052 or modified polypropene 15%～30%;
Compatilizer 5%～30%.
The present invention improves starch and polyacrylic consistency through compatilizer; Through the vegetables oil softening agent starch is plastified; The plastifying starch performance is stable; Four kinds of raw materials can interact, make starch of the present invention/Vestolen PP 7052 degradable composite material starch content than higher prerequisite under, embody excellent mechanical property.
As preferably, described starch/Vestolen PP 7052 degradable composite material, process by the raw material of following weight percentage:
Starch 50%～60%;
Vegetables oil softening agent 8%～12%;
Vestolen PP 7052 or modified polypropene 15%～25%;
Compatilizer 15%～25%.
Described starch is one or both in native starch, the treated starch.Described native starch is one or more in W-Gum, tapioca(flour), green starch, sweet potato starch, sweet potato starch, yam starch, wheat kind of starch, water caltrop starch, the Rhizoma Nelumbinis starch.Described treated starch is one or more in the two starch of modified by maleic acid anhydride graft starch, SULPHOSUCCINIC ACID ESTER, Ultra Tex 2, the two starch adipates of acetylize, the hydroxypropyl Staragel 90V.Described modified by maleic acid anhydride graft starch can specifically be selected the maleic anhydride graft W-Gum for use.Starch can biological degradation; Native starch be can complete biodegradable natural high moleculer eompound; Consider that from the cost and the degradability of starch/Vestolen PP 7052 degradable composite material not only cost is lower to select native starch for use, and degradability is good; Consider that from the mechanical property of starch/Vestolen PP 7052 degradable composite material treated starch more helps the raising of starch/Vestolen PP 7052 degradable composite material mechanical property when guaranteeing the certain degradation property of matrix material.
The present invention selects for use macromole vegetables oil softening agent that starch is plastified; The plastifying starch performance is stable; Macromole vegetables oil softening agent is difficult for separating out, and helps the toughness of the raising, particularly matrix material of starch/Vestolen PP 7052 degradable composite material mechanical property; And macromole vegetables oil softening agent plastifying starch is high temperature resistant, and product is inhibited from yellowing.Described vegetables oil softening agent is one or more in VT 18, peanut oil, Oleum Cocois, plam oil, oleum lini, Oleum Gossypii semen, Semen Maydis oil, sunflower seed oil, pine-seed oil, tung oil, the Viscotrol C.Further preferred; Described vegetables oil softening agent is a VT 18; The weight percentage of VT 18 is 10%; Adopting weight percentage is starch/Vestolen PP 7052 degradable composite material that 10% VT 18 not only can be prepared excellent performance, and VT 18 other oily costs are lower relatively, make the production cost of starch/Vestolen PP 7052 degradable composite material reduce greatly.
Described Vestolen PP 7052 can adopt the commercially available prod, selects for use the commercially available general trade mark to get final product.Modified polypropene also can be selected the commercially available general trade mark for use, specifically can adopt maleic anhydride inoculated polypropylene, and the Vestolen PP 7052 through maleic anhydride modified has better consistency with starch, has improved the consistency of Vestolen PP 7052 and starch.
Because two kinds of starch and Vestolen PP 7052 structurally exist notable difference to cause that consistency is not good between the two; The present invention improves starch and polyacrylic consistency through compatilizer, and described compatilizer is the multipolymer (EVA) of ethene-vinyl acetate, in the ethylene-acrylic acid copolymer (EAA) one or both.Further preferred, described compatilizer is the multipolymer of ethene-vinyl acetate, and the multipolymer of ethene-vinyl acetate can very well improve starch and polyacrylic consistency.
The present invention also provides the preparation method of a kind of starch/Vestolen PP 7052 degradable composite material, and preparation is simple, and is easy to implement, is easy to operate and control.
The preparation method of described starch/Vestolen PP 7052 degradable composite material may further comprise the steps:
Starch, vegetables oil softening agent, Vestolen PP 7052 and compatilizer are mixed, obtain mixed material; Perhaps starch, vegetables oil softening agent, modified polypropene and compatilizer are mixed, obtain mixed material; Mixed material is added to tie rod, pelletizing behind the melt blending in the twin screw extruder, obtains the particulate state hybrid resin; The particulate state hybrid resin obtains starch/Vestolen PP 7052 degradable composite material after drying treatment.
The screw slenderness ratio of described twin screw extruder is 35: 1～45: 1; The temperature of described melt blending is 160 ℃～180 ℃, and the vegetables oil softening agent plastifies starch, and the plastifying starch performance is stable, and the vegetables oil softening agent is difficult for separating out, raw material can be under 160 ℃～180 ℃ comparatively high tempss melt extrusion.
Starch of the present invention/Vestolen PP 7052 degradable composite material is applicable to fields such as Plastic Packaging Materials, agricultural mulching and disposable tableware; With starch/Vestolen PP 7052 degradable composite material is starting material, produces plastic packaging film, agricultural mulching and disposable tableware through existing processing technology.
Compared with prior art, the present invention has following advantage:
In starch of the present invention/Vestolen PP 7052 degradable composite material; Starch content is higher; Make starch of the present invention/Vestolen PP 7052 degradable composite material have degradability preferably; When adopting cheap, the native starch that is easy to obtain, starch of the present invention/Vestolen PP 7052 degradable composite material still has mechanical property and high thermal resistance preferably, and degradability is better simultaneously.The vegetables oil softening agent under given conditions can be by microbiological degradation, and is biodegradable.Thereby main raw material starch and the equal degradable of vegetables oil softening agent in starch of the present invention/Vestolen PP 7052 degradable composite material make starch of the present invention/Vestolen PP 7052 degradable composite material have degradability preferably.
Starch of the present invention/Vestolen PP 7052 degradable composite material; Improve starch and polyacrylic consistency through compatilizer, through the vegetables oil softening agent starch is plastified, the plastifying starch performance is stable; The vegetables oil softening agent is difficult for separating out; And vegetables oil softening agent plastifying starch is high temperature resistant, make raw material can be under 160 ℃～180 ℃ comparatively high tempss melt extrusion, product is inhibited from yellowing; Make the toughness and the shock resistance of starch of the present invention/Vestolen PP 7052 degradable composite material strengthen greatly, stable performance simultaneously.Four kinds of raw materials of the present invention can interact, make starch of the present invention/Vestolen PP 7052 degradable composite material starch content than higher prerequisite under, embody excellent mechanical property and certain high thermal resistance.
Starch/PP composite material of the present invention not only goes for fields such as Plastic Packaging Materials, agricultural mulching and disposable tableware; And the last major part of starch/PP composite material of the present invention can be by microbiological degradation in the soil and absorption; Environmental pollution is little, has good benefits in environment and social value.
The preparation method of starch of the present invention/Vestolen PP 7052 degradable composite material, preparation is simple, and is easy to implement; Be easy to operate and control, preparation cost is cheap, and excellent product performance is with stable; Be easy to suitability for industrialized production and have good economic benefits, have broad application prospects.
Embodiment
Following examples further describe the present invention, but the present invention is not limited to these embodiment.
Preparation example 1
With the W-Gum (weight percentage of moisture is 4.1%, Xingmao Corn Development Co., Ltd., Zhucheng) of 60g, the maleic anhydride (traditional Chinese medicines reagent) of 2.6g, the DMAC N,N (DMAc of 100mL; Traditional Chinese medicines reagent) and 20mL toluene (traditional Chinese medicines reagent) be added in the 250mL there-necked flask and stir, in 130 ℃ of following mechanical stirring 1h, the static upper strata solvent of removing; Add acetone then and stir the unreacted maleic anhydride of flush away; The static upper strata solvent of removing adds the static upper strata solvent of removing of acetone once more, adds after acetone removes the upper strata solvent and carry out 3 times altogether; Filter; Wash repeatedly 3 times with acetone again, put into vacuum drying oven dry 12h under 80 ℃ to the modified corn starch that obtains, obtain 60g maleic anhydride graft W-Gum.
Embodiment 1
Take by weighing the raw material of following weight part:
Maleic anhydride graft W-Gum 55 weight parts of preparation example 1 preparation; VT 18 (Aladdin reagent) 10 weight parts; Maleic anhydride inoculated polypropylene (model is GPM200A for general purpose grade, Ningbo NengZhiGuang New Materials Science Co., Ltd) 10 weight parts; Ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 25 weight parts.
After maleic anhydride graft W-Gum 55 weight parts, VT 18 10 weight parts, maleic anhydride inoculated polypropylene 10 weight parts and ethylene-vinyl acetate copolymer 25 weight parts were mixed, (mixed material was 160 ℃ through excess temperature successively, 170 ℃ then mixed material to be added to melt blending in the twin screw extruder; 170 ℃, 170 ℃, 175 ℃; 170 ℃, 170 ℃, each interval of 160 ℃ melt blending) the back tie rod; Pelletizing obtains the particulate state hybrid resin; The particulate state hybrid resin obtains starch/Vestolen PP 7052 degradable composite material after the drying treatment that dewaters.The screw slenderness ratio of the twin screw extruder of selecting for use is 40: 1.
The above-mentioned starch that obtains/Vestolen PP 7052 degradable composite material is added to injection moulding in the injection moulding machine, obtains the goods batten.200 ℃ of injection moulding district temperature, 45 ℃ of template region temperature.
Embodiment 2
Take by weighing the raw material of following weight part:
Maleic anhydride graft W-Gum 55 weight parts of preparation example 1 preparation; VT 18 (Aladdin reagent) 10 weight parts; Maleic anhydride inoculated polypropylene (model is GPM200A for general purpose grade, Ningbo NengZhiGuang New Materials Science Co., Ltd) 20 weight parts; Ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After maleic anhydride graft W-Gum 55 weight parts, VT 18 10 weight parts, maleic anhydride inoculated polypropylene 20 weight parts and ethylene-vinyl acetate copolymer 15 weight parts were mixed, (mixed material was 160 ℃ through excess temperature successively, 170 ℃ then mixed material to be added to melt blending in the twin screw extruder; 175 ℃, 170 ℃, 170 ℃; 170 ℃, 170 ℃, each interval of 160 ℃ melt blending) the back tie rod; Pelletizing obtains the particulate state hybrid resin; The particulate state hybrid resin obtains starch/Vestolen PP 7052 degradable composite material after the drying treatment that dewaters.The screw slenderness ratio of the twin screw extruder of selecting for use is 40: 1.
The above-mentioned starch that obtains/Vestolen PP 7052 degradable composite material is added to injection moulding in the injection moulding machine, obtains the goods batten.200 ℃ of injection moulding district temperature, 45 ℃ of template region temperature.
Embodiment 3
Take by weighing the raw material of following weight part:
Maleic anhydride graft W-Gum 55 weight parts of preparation example 1 preparation; VT 18 (Aladdin reagent) 10 weight parts, Vestolen PP 7052 20 (Exxon Mobil, model are 7684KN) weight part; Ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After maleic anhydride graft W-Gum 55 weight parts, VT 18 10 weight parts, Vestolen PP 7052 20 weight parts and ethylene-vinyl acetate copolymer 15 weight parts were mixed, (mixed material was 160 ℃ through excess temperature successively, 170 ℃ then mixed material to be added to melt blending in the twin screw extruder; 175 ℃, 180 ℃, 185 ℃; 175 ℃, 170 ℃, each interval of 160 ℃ melt blending) the back tie rod; Pelletizing obtains the particulate state hybrid resin; The particulate state hybrid resin obtains starch/Vestolen PP 7052 degradable composite material after the drying treatment that dewaters.The screw slenderness ratio of the twin screw extruder of selecting for use is 40: 1.
The above-mentioned starch that obtains/Vestolen PP 7052 degradable composite material is added to injection moulding in the injection moulding machine, obtains the goods batten.200 ℃ of injection moulding district temperature, 45 ℃ of template region temperature.
Embodiment 4
Take by weighing the raw material of following weight part:
Maleic anhydride graft W-Gum 60 weight parts of preparation example 1 preparation; VT 18 (Aladdin reagent) 10 weight parts, Vestolen PP 7052 (Exxon Mobil, model are 7684KN) 15 weight parts; Ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After maleic anhydride graft W-Gum 60 weight parts, VT 18 10 weight parts, Vestolen PP 7052 15 weight parts and ethylene-vinyl acetate copolymer 15 weight parts were mixed, (mixed material was 160 ℃ through excess temperature successively, 170 ℃ then mixed material to be added to melt blending in the twin screw extruder; 175 ℃, 170 ℃, 175 ℃; 170 ℃, 160 ℃, each interval of 160 ℃ melt blending) the back tie rod; Pelletizing obtains the particulate state hybrid resin; The particulate state hybrid resin obtains starch/Vestolen PP 7052 degradable composite material after the drying treatment that dewaters.The screw slenderness ratio of the twin screw extruder of selecting for use is 40: 1.
The above-mentioned starch that obtains/Vestolen PP 7052 degradable composite material is added to injection moulding in the injection moulding machine, obtains the goods batten.200 ℃ of injection moulding district temperature, 45 ℃ of template region temperature.
Embodiment 5
Take by weighing the raw material of following weight part:
Maleic anhydride graft W-Gum 60 weight parts of preparation example 1 preparation; VT 18 (Aladdin reagent) 10 weight parts, Vestolen PP 7052 (Exxon Mobil, model are 7684KN) 20 weight parts; Ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 10 weight parts.
After maleic anhydride graft W-Gum 60 weight parts, VT 18 10 weight parts, Vestolen PP 7052 20 weight parts and ethylene-vinyl acetate copolymer 10 weight parts were mixed, (mixed material was 160 ℃ through excess temperature successively, 170 ℃ then mixed material to be added to melt blending in the twin screw extruder; 175 ℃, 170 ℃, 175 ℃; 175 ℃, 160 ℃, each interval of 160 ℃ melt blending) the back tie rod; Pelletizing obtains the particulate state hybrid resin; The particulate state hybrid resin obtains starch/Vestolen PP 7052 degradable composite material after the drying treatment that dewaters.The screw slenderness ratio of the twin screw extruder of selecting for use is 40: 1.
The above-mentioned starch that obtains/Vestolen PP 7052 degradable composite material is added to injection moulding in the injection moulding machine, obtains the goods batten.200 ℃ of injection moulding district temperature, 45 ℃ of template region temperature.
Embodiment 6
Take by weighing the raw material of following weight part:
Two starch (Zhangjiakou Shen Zhou starch Science and Technology Ltd.) 60 weight parts of SULPHOSUCCINIC ACID ESTER; VT 18 (Aladdin reagent) 10 weight parts, Vestolen PP 7052 (Exxon Mobil, model are 7684KN) 15 weight parts; Ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After two starch 60 weight parts of SULPHOSUCCINIC ACID ESTER, VT 18 10 weight parts, Vestolen PP 7052 15 weight parts and ethylene-vinyl acetate copolymer 15 weight parts were mixed, (mixed material was 160 ℃ through excess temperature successively, 170 ℃ then mixed material to be added to melt blending in the twin screw extruder; 175 ℃, 170 ℃, 175 ℃; 175 ℃, 160 ℃, each interval of 160 ℃ melt blending) the back tie rod; Pelletizing obtains the particulate state hybrid resin; The particulate state hybrid resin obtains starch/Vestolen PP 7052 degradable composite material after the drying treatment that dewaters.The screw slenderness ratio of the twin screw extruder of selecting for use is 40: 1.
The above-mentioned starch that obtains/Vestolen PP 7052 degradable composite material is added to injection moulding in the injection moulding machine, obtains the goods batten.200 ℃ of injection moulding district temperature, 45 ℃ of template region temperature.
Embodiment 7
Take by weighing the raw material of following weight part:
Two starch adipate (Zhangjiakou Shen Zhou starch Science and Technology Ltd.) 60 weight parts of acetylize; VT 18 (Aladdin reagent) 10 weight parts, Vestolen PP 7052 (Exxon Mobil, model are 7684KN) 15 weight parts; Ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After two starch adipate 60 weight parts of acetylize, VT 18 10 weight parts, Vestolen PP 7052 15 weight parts and ethylene-vinyl acetate copolymer 15 weight parts were mixed, (mixed material was 160 ℃ through excess temperature successively, 170 ℃ then mixed material to be added to melt blending in the twin screw extruder; 175 ℃, 170 ℃, 175 ℃; 175 ℃, 160 ℃, each interval of 160 ℃ melt blending) the back tie rod; Pelletizing obtains the particulate state hybrid resin; The particulate state hybrid resin obtains starch/Vestolen PP 7052 degradable composite material after the drying treatment that dewaters.The screw slenderness ratio of the twin screw extruder of selecting for use is 40: 1.
The above-mentioned starch that obtains/Vestolen PP 7052 degradable composite material is added to injection moulding in the injection moulding machine, obtains the goods batten.200 ℃ of injection moulding district temperature, 45 ℃ of template region temperature.
Embodiment 8
The vegetables oil softening agent adopts peanut oil among the embodiment 8, and other are with embodiment 7.
Embodiment 7 compares with embodiment 8; Adopt VT 18 to have better properties as the starch/Vestolen PP 7052 degradable composite material of vegetables oil softening agent preparation; And from the marketization and industrialized angle; Adopt VT 18 also more cheap, the production cost of starch/Vestolen PP 7052 degradable composite material is lower.
Embodiment 9
Take by weighing the raw material of following weight part:
Two starch adipate (Zhangjiakou Shen Zhou starch Science and Technology Ltd.) 58 weight parts of acetylize; VT 18 (Aladdin reagent) 12 weight parts, Vestolen PP 7052 (Exxon Mobil, model are 7684KN) 15 weight parts; Ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After two starch adipate 58 weight parts of acetylize, VT 18 12 weight parts, Vestolen PP 7052 15 weight parts and ethylene-vinyl acetate copolymer 15 weight parts were mixed, (mixed material was 160 ℃ through excess temperature successively, 170 ℃ then mixed material to be added to melt blending in the twin screw extruder; 175 ℃, 170 ℃, 175 ℃; 175 ℃, 160 ℃, each interval of 160 ℃ melt blending) the back tie rod; Pelletizing obtains the particulate state hybrid resin; The particulate state hybrid resin obtains starch/Vestolen PP 7052 degradable composite material after the drying treatment that dewaters.The screw slenderness ratio of the twin screw extruder of selecting for use is 40: 1.
The above-mentioned starch that obtains/Vestolen PP 7052 degradable composite material is added to injection moulding in the injection moulding machine, obtains the goods batten.200 ℃ of injection moulding district temperature, 45 ℃ of template region temperature.
Embodiment 10
Take by weighing the raw material of following weight part:
Two starch adipate (Zhangjiakou Shen Zhou starch Science and Technology Ltd.) 58 weight parts of acetylize; VT 18 (Aladdin reagent) 8 weight parts, Vestolen PP 7052 (Exxon Mobil, model are 7684KN) 19 weight parts; Ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After two starch adipate 58 weight parts of acetylize, VT 18 12 weight parts, Vestolen PP 7052 15 weight parts and ethylene-vinyl acetate copolymer 15 weight parts were mixed, (mixed material was 160 ℃ through excess temperature successively, 170 ℃ then mixed material to be added to melt blending in the twin screw extruder; 175 ℃, 170 ℃, 175 ℃; 175 ℃, 160 ℃, each interval of 160 ℃ melt blending) the back tie rod; Pelletizing obtains the particulate state hybrid resin; The particulate state hybrid resin obtains starch/Vestolen PP 7052 degradable composite material after the drying treatment that dewaters.The screw slenderness ratio of the twin screw extruder of selecting for use is 40: 1.
The above-mentioned starch that obtains/Vestolen PP 7052 degradable composite material is added to injection moulding in the injection moulding machine, obtains the goods batten.200 ℃ of injection moulding district temperature, 45 ℃ of template region temperature.
Embodiment 9, embodiment 10 compare with embodiment 7, and the key distinction is the weight part of VT 18, and visible weight percentage at VT 18 is 10% o'clock, and the starch of preparation/Vestolen PP 7052 degradable composite material has better properties.
Embodiment 11
Take by weighing the raw material of following weight part:
(weight percentage of moisture is 4.1% to W-Gum; Xingmao Corn Development Co., Ltd., Zhucheng) 50 weight parts; VT 18 (Aladdin reagent) 10 weight parts, Vestolen PP 7052 (Exxon Mobil, model are 7684KN) 20 weight parts; Ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 20 weight parts.
After W-Gum 50 weight parts, VT 18 10 weight parts, Vestolen PP 7052 20 weight parts and ethylene-vinyl acetate copolymer 20 weight parts were mixed, (mixed material was 165 ℃ through excess temperature successively, 165 ℃ then mixed material to be added to melt blending in the twin screw extruder; 170 ℃, 170 ℃, 170 ℃; 165 ℃, 160 ℃, each interval of 160 ℃ melt blending) the back tie rod; Pelletizing obtains the particulate state hybrid resin; The particulate state hybrid resin obtains starch/Vestolen PP 7052 degradable composite material after the drying treatment that dewaters.The screw slenderness ratio of the twin screw extruder of selecting for use is 40: 1.
The above-mentioned starch that obtains/Vestolen PP 7052 degradable composite material is added to injection moulding in the injection moulding machine, obtains the goods batten.200 ℃ of injection moulding district temperature, 45 ℃ of template region temperature.
Embodiment 12
Take by weighing the raw material of following weight part:
(weight percentage of moisture is 4.1% to W-Gum; Xingmao Corn Development Co., Ltd., Zhucheng) 55 weight parts; VT 18 (Aladdin reagent) 10 weight parts, Vestolen PP 7052 20 weight parts (Exxon Mobil, model are 7684KN); Ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After W-Gum 55 weight parts, VT 18 10 weight parts, Vestolen PP 7052 20 weight parts and ethylene-vinyl acetate copolymer 15 weight parts were mixed, (mixed material was 165 ℃ through excess temperature successively, 165 ℃ then mixed material to be added to melt blending in the twin screw extruder; 170 ℃, 170 ℃, 170 ℃; 165 ℃, 160 ℃, each interval of 160 ℃ melt blending) the back tie rod; Pelletizing obtains the particulate state hybrid resin; The particulate state hybrid resin obtains starch/Vestolen PP 7052 degradable composite material after the drying treatment that dewaters.The screw slenderness ratio of the twin screw extruder of selecting for use is 40: 1.
The above-mentioned starch that obtains/Vestolen PP 7052 degradable composite material is added to injection moulding in the injection moulding machine, obtains the goods batten.200 ℃ of injection moulding district temperature, 45 ℃ of template region temperature.
Starch/Vestolen PP 7052 the degradable composite material of embodiment 1～10 preparation is carried out impact property test (four groups of experiments are averaged for notch impact test, pendulum 5.5J) according to ASTM D256-2006, and its test result is as shown in table 1.Embodiment 11～12 prepared starch/Vestolen PP 7052 degradable composite materials are carried out shock resistance test (notch impact test according to ASTM D 256-2006; Pendulum 5.5J; Four groups of experiments are averaged); Carry out the test (four groups of experiments are averaged) of elongation at break and tensile strength according to GB1040-2006, its test result is as shown in table 2.
Table 1
Table 2
| Embodiment | 11 | 12 |
| Shock strength (KJ/m 2) | 16.5 | 14.3 |
| Elongation at break (%) | 120 | 90 |
| Tensile strength (MPa) | 11 | 14 |
Claims (10)
1. starch/Vestolen PP 7052 degradable composite material, process by the raw material of following weight percentage:
Starch 50%～70%;
Vegetables oil softening agent 5%～15%;
Vestolen PP 7052 or modified polypropene 15%～30%;
Compatilizer 5%～30%.
2. starch according to claim 1/Vestolen PP 7052 degradable composite material is characterized in that, is processed by the raw material of following weight percentage:
Starch 50%～60%;
Vegetables oil softening agent 8%～12%;
Vestolen PP 7052 or modified polypropene 15%～25%;
Compatilizer 15%～25%.
3. starch according to claim 1 and 2/Vestolen PP 7052 degradable composite material is characterized in that, described starch is one or both in native starch, the treated starch.
4. starch according to claim 3/Vestolen PP 7052 degradable composite material; It is characterized in that described native starch is one or more in W-Gum, tapioca(flour), green starch, sweet potato starch, sweet potato starch, yam starch, wheat kind of starch, water caltrop starch, the Rhizoma Nelumbinis starch.
5. starch according to claim 3/Vestolen PP 7052 degradable composite material; It is characterized in that described treated starch is one or more in the two starch of modified by maleic acid anhydride graft starch, SULPHOSUCCINIC ACID ESTER, Ultra Tex 2, the two starch adipates of acetylize, the hydroxypropyl Staragel 90V.
6. starch according to claim 1 and 2/Vestolen PP 7052 degradable composite material; It is characterized in that described vegetables oil softening agent is one or more in VT 18, peanut oil, Oleum Cocois, plam oil, oleum lini, Oleum Gossypii semen, Semen Maydis oil, sunflower seed oil, pine-seed oil, tung oil, the Viscotrol C.
7. starch according to claim 1 and 2/Vestolen PP 7052 degradable composite material is characterized in that, described vegetables oil softening agent is a VT 18, and the weight percentage of VT 18 is 10%.
8. starch according to claim 1 and 2/Vestolen PP 7052 degradable composite material is characterized in that, described compatilizer is the multipolymer of ethene-vinyl acetate, in the ethylene-acrylic acid copolymer one or both.
9. according to the preparation method of each described starch/Vestolen PP 7052 degradable composite material of claim 1～8, may further comprise the steps:
Starch, vegetables oil softening agent, Vestolen PP 7052 and compatilizer are mixed, obtain mixed material; Perhaps starch, vegetables oil softening agent, modified polypropene and compatilizer are mixed, obtain mixed material; Mixed material is added to tie rod, pelletizing behind the melt blending in the twin screw extruder, obtains the particulate state hybrid resin; The particulate state hybrid resin obtains starch/Vestolen PP 7052 degradable composite material after drying treatment.
10. the preparation method of starch according to claim 9/Vestolen PP 7052 degradable composite material is characterized in that, the screw slenderness ratio of described twin screw extruder is 35～45: 1; The temperature of described melt blending is 160 ℃～180 ℃.
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Inventor after: Xiong Zhu Inventor after: Tan Diexi Inventor after: Zhu Jin Inventor after: Tang Zhaobin Inventor after: Zhang Chuanzhi Inventor after: Yang Yong Inventor after: Zhang Lisheng Inventor before: Xiong Zhu Inventor before: Zhu Jin Inventor before: Tang Zhaobin Inventor before: Zhang Chuanzhi Inventor before: Yang Yong Inventor before: Zhang Lisheng |
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