CN111808303A - Application of starch master batch composition in preparation of degradable material - Google Patents
Application of starch master batch composition in preparation of degradable material Download PDFInfo
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- CN111808303A CN111808303A CN201910295042.5A CN201910295042A CN111808303A CN 111808303 A CN111808303 A CN 111808303A CN 201910295042 A CN201910295042 A CN 201910295042A CN 111808303 A CN111808303 A CN 111808303A
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- starch
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- plasticizer
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- 229920002472 Starch Polymers 0.000 title claims abstract description 109
- 235000019698 starch Nutrition 0.000 title claims abstract description 105
- 239000008107 starch Substances 0.000 title claims abstract description 104
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 27
- 239000012141 concentrate Substances 0.000 claims abstract description 22
- 239000004014 plasticizer Substances 0.000 claims abstract description 20
- 239000000314 lubricant Substances 0.000 claims abstract description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 55
- 239000004698 Polyethylene Substances 0.000 claims description 27
- 239000001993 wax Substances 0.000 claims description 22
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 18
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 18
- 229920002261 Corn starch Polymers 0.000 claims description 15
- 239000008120 corn starch Substances 0.000 claims description 15
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 8
- 239000000600 sorbitol Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 7
- 229920001592 potato starch Polymers 0.000 claims description 7
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- 229940100445 wheat starch Drugs 0.000 claims description 4
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 240000003183 Manihot esculenta Species 0.000 claims description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002671 adjuvant Substances 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims description 3
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 abstract description 18
- 239000004033 plastic Substances 0.000 abstract description 18
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 235000011187 glycerol Nutrition 0.000 description 18
- 238000012360 testing method Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000004806 packaging method and process Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229920000704 biodegradable plastic Polymers 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000010096 film blowing Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229920001896 polybutyrate Polymers 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229920006238 degradable plastic Polymers 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 241000195974 Selaginella Species 0.000 description 1
- 229920008262 Thermoplastic starch Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000004628 starch-based polymer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2423/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of biodegradable materials, and discloses an application of a starch master batch composition in preparation of a degradable material. Based on the total weight of the starch concentrate composition, the starch concentrate composition comprises: 30-70 wt% of starch, 5-20 wt% of plasticizer, 8-35 wt% of carrier, 2-15 wt% of compatilizer, 1-5 wt% of lubricant and 0.1-1 wt% of auxiliary agent. The starch master batch composition provided by the invention can further improve the addition amount of starch in a degradable material by optimizing the components and the proportion, saves the cost, ensures excellent plastic performance of the prepared product and further improves the environmental protection performance of the product.
Description
Technical Field
The invention relates to the field of biodegradable materials, in particular to an application of a starch master batch composition in preparation of a degradable material.
Background
With the rapid development of Chinese economy and electronic commerce, the demand and the use amount of express packaging bags are increased rapidly. The existing express packaging bag is mainly used for conveying files, goods and the like in the express industry, but the disposable packaging bag is mainly a plastic packaging bag made of polyethylene and other materials, and has the characteristics of low cost, convenience in use and good waterproof performance.
Express delivery wrapping bag when having brought very big convenience for people's life, along with the increase of use amount, make this kind of disposable wrapping bag abandonment volume sharply increase, however, because the difficult decomposition of polyethylene is retrieved, its discarded object becomes harmful rubbish, the polluted environment, a large amount of abandonment plastic bags have become serious problem, simultaneously, along with the improvement of national environmental standard, also further improve to express delivery industry wrapping bag's environmental protection requirement, consequently, the urgent need provide a degradable plastics in order to solve a great deal of problems that current express delivery wrapping bag causes.
Therefore, in the prior art, a biodegradable material is mostly adopted to alleviate the problem, for example, CN108285622A discloses a biodegradable material and a preparation method thereof, which specifically discloses that the biodegradable material comprises the following raw materials in parts by weight: 20-50% of material A, 40-60% of material B and 20-40% of PBAT thermoplastic biodegradable plastic, wherein the material A comprises the following raw materials in parts by weight: 40-60% of PBAT thermoplastic biodegradable plastic, 78-50% of PLA30 and 8-15% of inorganic filler; the material B comprises the following raw materials in parts by weight: 40-60% of PBAT thermoplastic biodegradable plastic and 40-60% of starch master batch, wherein the starch master batch comprises the following raw materials in parts by weight: 60-70% of starch, 1-3% of coupling agent, 1-3% of paraffin, 25-30% of glycerol, 0.1-0.3% of citric acid and 2-5% of epoxidized soybean oil, the prepared biodegradable material has high degradation speed and good barrier property, and after being prepared into a film, the longitudinal elongation is 150.22%, the strength is 18.27MPa, the transverse elongation is 237.12%, and the strength is 12.49 MPa; CN104119647A discloses a full-biodegradable composition with high starch content and a preparation method thereof, and particularly discloses a full-biodegradable composition which is prepared from 10-80 parts of full-biodegradable thermoplastic starch master batch, 20-90 parts of biodegradable polyester and 0.3-5 parts of compatilizer, wherein the provided full-biodegradable composition has high starch content and good compatibility of starch and a matrix, the mechanical property of the material in the long-time storage process is ensured, and the cost of a film product prepared from the composition can be greatly reduced; CN101724178A discloses a biological potato starch degradable plastic master batch, a preparation method and an application thereof, wherein the plastic master batch comprises the following components by weight: 70-80% of refined potato starch, 7-10% of toughening agent, 0.5-2% of initiator, 4-7% of modifier, 1-3% of plasticizer and 3-6% of lubricating processing aid, wherein the prepared master batch product has certain strength and thermoplastic processing performance and can be used for processing various film products, blow molding products and injection molding products in different addition amounts; CN103342873A discloses an easily degradable environment-friendly plastic, which comprises the following components in parts by weight: 40-70 parts of ABS; 3-8 parts of an interface coupling agent; 3-10 parts of a toughening agent; 0.5-1.0 part by weight of dispersing lubricant; 5-10 parts of starch; 10-15 parts of polyethylene. The prepared easily degradable environment-friendly plastic has excellent easily degradable environment-friendly property and can be widely used in a plurality of industries; meanwhile, in the existing starch-based plastic, especially for preparing various plastic bag products, from the aspects of production cost, aging, processing convenience and the like, starch or starch master batches are usually directly used, and the starch master batches are already produced in large scale by manufacturers, but when the plastic bag is made, the addition amount of the starch master batches in the existing process cannot exceed 45% (the addition amount of the starch cannot exceed 25%), otherwise, the performance of the produced plastic is seriously attenuated.
Considering that the use of starch masterbatch can improve the degradation performance of starch plastics, and the cost of starch masterbatch is relatively low, how to further increase the content of starch masterbatch in the raw material formulation and avoid the degradation of the plastic performance is still the primary problem that troubles the practical production and application.
Disclosure of Invention
The invention aims to overcome the problems in the prior art, and provides the application of the starch master batch composition in the preparation of the degradable material.
In order to achieve the above object, the present invention provides an application of a starch masterbatch composition in preparing a degradable material, wherein the starch masterbatch composition comprises, based on the total weight of the starch masterbatch composition:
30-70 wt% of starch, 5-20 wt% of plasticizer, 8-35 wt% of carrier, 2-15 wt% of compatilizer, 1-5 wt% of lubricant and 0.1-1 wt% of auxiliary agent.
Preferably, the starch concentrate composition comprises, based on the total weight of the starch concentrate composition:
45-70 wt% of starch, 8-16 wt% of plasticizer, 8-30 wt% of carrier, 3-12 wt% of compatilizer, 1-3 wt% of lubricant and 0.1-1 wt% of auxiliary agent.
Preferably, the starch concentrate composition comprises, based on the total weight of the starch concentrate composition:
50-65 wt% of starch, 10-14 wt% of plasticizer, 8-25 wt% of carrier, 6-10 wt% of compatilizer, 1-2 wt% of lubricant and 0.3-0.5 wt% of auxiliary agent.
Preferably, the starch is one or more of wheat starch, corn starch, tapioca starch and potato starch.
Preferably, the plasticizer is one or more of glycerol, glycerol monostearate, sorbitol, triethanolamine and urea.
Preferably, the carrier is one or a combination of LLDPE, EAA and EVA.
Preferably, the LLDPE, EAA and EVA have a melt index in the range of 10-100g/10 min.
Preferably, the LLDPE, EAA, EVA have melt indices in the range of 20-50g/10 min.
Preferably, the compatibilizer is a grafted combination of one or more selected from LDPE and POE and one or more selected from maleic anhydride, itaconic anhydride, and substituted maleic anhydride.
Preferably, the compatilizer is a composition of LDPE-g-MA and POE-g-MA, wherein the weight ratio of the LDPE-g-MA to the POE-g-MA is 1: 0.5-2.
Preferably, the LDPE-g-MA grafting rate is more than 0.5%.
Preferably, the POE-g-MA grafting rate is more than 0.5 percent.
Preferably, the lubricant is one or more of PE wax, oxidized PE wax, calcium stearate, and zinc stearate.
Preferably, the adjuvant is selected from the group consisting of antioxidants and antimicrobial modifiers.
In the application of the starch master batch composition in preparing the degradable material, the components and the proportion of the starch master batch composition are optimized, and the addition amount of starch in the degradable material can be increased, so that the production cost is further saved;
the starch-based plastic product prepared from the starch master batch composition provided by the invention has excellent plastic performance; the packaging bag is suitable for packaging products, is particularly suitable for various packaging bags and/or sealing bags, and is particularly suitable for express bags, hand bags, vest bags, rope-penetrating bags, flat bags, buckle bags, zipper bags, edge sealing bags, hand bags, rope drawing bags and the like.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an SEM photograph of a stretched cross-section of S1 in example;
FIG. 2 is an SEM photograph of a stretched cross-section of S2 in example;
FIG. 3 is an SEM photograph of a stretched cross-section of S3 in example.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides an application of a starch master batch composition in preparing a degradable material, wherein the starch master batch composition comprises the following components by taking the total weight of the starch master batch composition as a reference:
30-70 wt% of starch, 5-20 wt% of plasticizer, 8-35 wt% of carrier, 2-15 wt% of compatilizer, 1-5 wt% of lubricant and 0.1-1 wt% of auxiliary agent.
The addition amount of the starch in the bio-based environment-friendly degradable material or product is increased through the optimized components and the proportion of the starch master batch composition, so that the production cost and the environment-friendly performance are further saved.
In the present invention, in order to further increase the addition amount of starch in the subsequent product, preferably, the starch masterbatch composition contains, based on the total weight of the starch masterbatch composition:
45-70 wt% of starch, 8-16 wt% of plasticizer, 8-30 wt% of carrier, 3-12 wt% of compatilizer, 1-3 wt% of lubricant and 0.1-1 wt% of auxiliary agent.
In the present invention, in order to further increase the addition amount of starch in the subsequent product, preferably, the starch masterbatch composition contains, based on the total weight of the starch masterbatch composition:
50-65 wt%, plasticizer 10-14 wt%, carrier 8-25 wt%, compatilizer 6-10 wt%, lubricant 1-2 wt%, and auxiliary agent 0.3-0.5 wt%.
In the present invention, the kind of the above starch is not particularly limited, and may be various commercially available starches, and in the present invention, it is preferable that the starch is one or more of wheat starch, corn starch, tapioca starch and potato starch. The source of the starch used in the present invention is not particularly limited, and may be deposited grain or industrial grain, or may be industrial grade or food grade, and those skilled in the art can determine the kind of the starch to be used according to market and industry requirements, and in the method of the present invention, industrial grade deposited grain is preferably selected.
The plasticizer is not particularly limited, and may be various plasticizers commonly used in the art, and may be determined by those skilled in the art according to actual use requirements, such as alcohols, esters, and the like, and in the present invention, in order to increase the addition amount of starch in subsequent products and ensure excellent performance of the products, preferably, the plasticizer is one or more of glycerol, glycerol monostearate, sorbitol, triethanolamine, and urea.
The carrier is not particularly limited, and may be various carriers commonly used in the art, and in the present invention, in order to ensure the fluidity of the final starch concentrate, it is preferable that the carrier is one or a combination of more of LLDPE, EAA and EVA.
In order to further increase the addition amount of starch in subsequent products and ensure the excellent performance of the products, in the invention, the LLDPE, EAA and EVA preferably have a melt index range of 10-100g/10 min.
In order to further increase the addition amount of starch in subsequent products and ensure excellent performance of the products, in the invention, the LLDPE, EAA and EVA preferably have a melt index in the range of 20-50g/10 min.
In order to improve the dispersibility of the starch in the starch masterbatch, in the present invention, preferably, the compatibilizer is a graft combination of one or more selected from LDPE and POE and one or more selected from maleic anhydride, itaconic anhydride, and substituted maleic anhydride.
In order to further increase the adding amount of starch in subsequent products and ensure the excellent performance of the products, in the invention, the compatilizer is a composition of LDPE-g-MA and POE-g-MA, wherein the weight ratio of the LDPE-g-MA to the POE-g-MA is 1: 0.5-2.
In the present invention, the LDPE-g-MA graft ratio is preferably 0.5% or more, and in the embodiment of the present invention, the graft ratio is 0.6 to 1.0%.
In the present invention, the compatibilizer is preferably POE-g-MA, and the grafting ratio is 0.5% or more, and in the embodiment of the present invention, the grafting ratio is 0.6 to 1.0%.
In order to improve the processability of the starch masterbatch composition during granulation, the lubricant is preferably one or more of PE wax, oxidized PE wax, calcium stearate and zinc stearate.
The above-mentioned auxiliary agents are not particularly limited, and may be selected to be compounded according to specific use requirements, in order to increase the addition amount of starch in subsequent products and ensure the excellent performance of the products, preferably, the auxiliary agents are selected from antioxidants and antibacterial modifiers, in one embodiment of the present invention, a combination of a compounded antioxidant comprising an antioxidant 1076 and an antioxidant 168 and an antibacterial modifier comprising vanillin is selected, and the amount ratio of the antioxidant to the antibacterial modifier in the combination can be determined by those skilled in the art according to actual needs.
In a specific embodiment of the present invention, the starch masterbatch composition may be prepared into starch masterbatch for use, and the preparation method is not particularly limited, and may be various preparation methods conventionally adopted by those skilled in the art, and will not be described herein again. In a specific embodiment of the invention, the preparation is carried out according to the following steps:
1) adding the starch and the plasticizer into a high-speed mixer, and stirring for 15-30 minutes at normal temperature;
2) adding the rest components, stirring at normal temperature for 10-15 min, and discharging;
3) and extruding and granulating by using a parallel double-screw granulator unit to obtain the starch master batch.
In the specific embodiment of the invention, the temperature of each section of the double-screw granulator unit is 90-175 ℃, and the screw rotating speed is 250-400 rpm.
The particle size of the starch concentrate is not particularly limited, and in the method of the present invention, the particle size of the starch concentrate is preferably 10 to 30 μm, in consideration of the actual conditions of the starch concentrate production equipment and convenience in the subsequent use of the starch concentrate.
The particle size of the starch concentrate is not particularly limited, and the moisture content of the starch concentrate is preferably 0.1-0.5 wt% in the method of the present invention, in consideration of the actual conditions of the starch concentrate production equipment and convenience in the subsequent use of the starch concentrate.
The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
The performance test method comprises the following steps:
tensile strength, tearing strength, pendulum impact resistance and puncture strength test: and testing according to a corresponding national standard testing method.
And (3) testing tensile property: according to the test of GB/T1040.3-2006, the sample adopts type 2, the length is 150mm, the width is 15mm, and the test speed is 200 mm/min. Detecting data of the sample in the longitudinal direction and the transverse direction;
and (3) testing the tearing strength: the method is carried out according to the regulation of GB/T16578.2-2009. Detecting data of the sample in the longitudinal direction and the transverse direction;
pendulum impact resistance: testing according to GB/T8809-2015 standard;
puncture strength: testing according to GB/T10004-2008 standard;
the unit of tensile strength is N, the unit of tensile strength is MPa, the unit of elongation at break is%, the unit of pendulum impact resistance is J, and the unit of puncture strength is N.
Example 1
50 wt% of corn starch, 10 wt% of glycerol, 26 wt% of LLDPE, 1 wt% of PE wax, 8 wt% of LDPE-g-MA + 4 wt% of POE-g-MA and 1 wt% of auxiliary agent.
Example 2
50 wt% of corn starch, 10 wt% of glycerol, 26 wt% of LLDPE, 1 wt% of PE wax, 6 wt% of LDPE-g-MA + 6 wt% of POE-g-MA and 1 wt% of auxiliary agent.
Example 3
50 wt% of corn starch, 10 wt% of glycerol, 26 wt% of LLDPE, 1 wt% of PE wax, 4 wt% of LDPE-g-MA + 8 wt% of POE-g-MA and 1 wt% of auxiliary agent.
Example 4
60 wt% of corn starch, 7 wt% of glycerol, 7 wt% of sorbitol, 16 wt% of EAA, 2 wt% of PE wax, 3.5 wt% of LDPE-g-MA3.5wt%, 3.5 wt% of POE-g-MA and 1 wt% of auxiliary agent.
Example 5
60 wt% of corn starch, 7 wt% of glycerin, 7 wt% of sorbitol, 16 wt% of EAA, 2 wt% of oxidized PE wax, 3.5 wt% of LDPE-g-MA, 3.5 wt% of POE-g-MA and 1 wt% of auxiliary agent.
Example 6
60 wt% of corn starch, 14 wt% of glycerol, 16 wt% of EAA, 2 wt% of oxidized PE wax, 3.5 wt% of LDPE-g-MA, 3.5 wt% of POE-g-MA and 1 wt% of auxiliary agent.
Example 7
65 wt% of corn starch, 15 wt% of glycerol, 11.7 wt% of EAA, 2 wt% of oxidized PE wax, 3 wt% of LDPE-g-MA + 3 wt% of POE-g-MA and 0.3 wt% of auxiliary agent.
Example 8
70 wt% of corn starch, 16 wt% of glycerol, 8 wt% of LLDPE, 2 wt% of oxidized PE wax, 1.5 wt% of LDPE-g-MA, 1.5 wt% of POE-g-MA1.5 wt% and 1 wt% of auxiliary agent.
Example 9
30 wt% of corn starch, 7 wt% of glycerol, 16 wt% of EAA, 16 wt% of EVA, 16 wt% of LLDPE, 16 wt% of PE wax, 1 wt% of LDPE-g-MA, 6.5 wt% of POE-g-MA and 1 wt% of auxiliary agent.
Example 10
55 wt% of wheat starch, 12 wt% of glycerol, 27 wt% of LLDPE, 2 wt% of PE wax, 1.5 wt% of LDPE-g-MA, 1.5 wt% of POE-g-MA and 1 wt% of auxiliary agent.
Example 11
55 wt% of potato starch, 6 wt% of glycerol, 6 wt% of sorbitol, 13.5 wt% of EAA, 13.5 wt% of EVA, 2 wt% of oxidized PE wax, 1.5 wt% of LDPE-g-MA, 1.5 wt% of POE-g-MA and 1 wt% of auxiliary agent.
Example 12
40 wt% of potato starch, 8 wt% of glycerol, 15 wt% of EAA, 10 wt% of EVA, 22 wt% of LLDPE, 1 wt% of PE wax, 1.5 wt% of LDPE-g-MA, 1.5 wt% of POE-g-MA and 1 wt% of auxiliary agent.
Comparative example 1
55 wt% of corn starch, 12 wt% of glycerol, 30 wt% of LLDPE, 2 wt% of PE wax and 1 wt% of auxiliary agent.
Comparative example 2
60 wt% of corn starch, 8 wt% of glycerol, 8 wt% of sorbitol, 20 wt% of EAA, 2 wt% of oxidized PE wax, 0.5 wt% of LDPE-g-MA, 0.5 wt% of POE-g-MA and 1 wt% of auxiliary agent.
Comparative example 3 corn starch 60 wt%, glycerin 8 wt% + sorbitol 8 wt%, EAA 16 wt%, LDPE-g-MA3.5wt% + POE-g-MA 3.5 wt%, adjuvant 1 wt%.
Preparation of starch concentrate
According to a specific implementation mode, firstly, starch and plasticizer are added into a high-speed mixer according to the proportion shown in examples 1-12 and comparative examples 1-3 and are stirred for 15 minutes at normal temperature; then adding the carrier, the compatilizer, the lubricant and the auxiliary agent according to the proportion, continuously stirring for 10 minutes at normal temperature, and discharging for later use;
extruding and granulating by using a parallel double-screw granulator set, and setting the temperature of each area of the double-screw extruder as follows: first zone 90 deg.C, second zone 140 deg.C, third zone 145 deg.C, fourth zone 150 deg.C, fifth zone 150 deg.C, sixth zone 150 deg.C, seventh zone 150 deg.C, eighth zone 150 deg.C, ninth zone 150 deg.C, tenth zone 150 deg.C, eleventh zone 150 deg.C, twelfth zone 140 deg.C, thirteenth zone 120 deg.C, and head 120 deg.C; setting the rotation speed of the screw at 380rpm to obtain starch master batches M1-12 and D1-3 with the grain diameter of 10-30 mu M.
TABLE 1 Effect of different lubricants on the processability of the granulation Process
| Lubricant agent | Pressure of granulation die head | |
| Example 1 | 2% PE wax | 4.0-6.0/12 |
| Example 2 | 2% oxidized PE wax | 2.5-3.5/12 |
| Comparative example 3 | Without addition of PE wax | The blocking die head can not be stably manufacturedGranule |
Preparation of Plastic products S1-S12 and SD1-SD3
Respectively taking the prepared light powder master batches M1-M12 and D1-D3(60 parts by weight) and PE (40 parts by weight) to prepare plastics according to the following modes:
after mixing the raw materials, putting the raw materials into a film blowing machine for film blowing, and setting the temperature of each area of the film blowing machine as follows: the first zone is 160 ℃, the second zone is 165 ℃, the third zone is 170 ℃, the fourth zone is 170 ℃, the fifth zone is 170 ℃, the upper die head is 170 ℃ and the lower die head is 170 ℃ to obtain plastic products S1-S12 and SD1-SD 3; FIG. 1 is an SEM photograph of an S1 stretched section, wherein starch particles have small particle size, are uniformly dispersed, have no obvious agglomeration and have excellent film stretching performance; FIG. 2 is an SEM photograph of an S2 stretched section, wherein the starch particles have small particle size, are uniformly dispersed, have no obvious agglomeration and have excellent film stretching performance; FIG. 3 is an SEM photograph of the stretched cross section of S3, wherein the starch particles have small particle size, are uniformly dispersed, have no obvious agglomeration and have excellent film stretching performance.
The above-mentioned tests S1-S12 and SD1-SD3 were carried out, and the test results are shown in Table 2 below.
TABLE 2
As can be seen from the above Table 2, the film products prepared by using the starch concentrate of the present invention have excellent plastic properties, and the properties of the products are not reduced by the increase of the starch concentrate.
The starch used in the above examples was a commercially available conventional product, the plasticizer was a plasticizer of whole plant origin, the melt index of LLDPE was 20g/10min, the melt index of EVA was 50g/10min, the melt index of EAA was 20g/10min, the graft ratio of LDPE-g-MA was 0.6% (purchased from Chinese Korea, model KHPE-2310), and the graft ratio of POE-g-MA was 0.6% (purchased from southern Selaginella Foshanensis, model PC-28 CF).
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The application of a starch masterbatch composition in preparing a degradable material is characterized in that the starch masterbatch composition contains, based on the total weight of the starch masterbatch composition:
30-70 wt% of starch, 5-20 wt% of plasticizer, 8-35 wt% of carrier, 2-15 wt% of compatilizer, 1-5 wt% of lubricant and 0.1-1 wt% of auxiliary agent.
2. The use of claim 1, wherein the starch concentrate composition comprises, based on the total weight of the starch concentrate composition:
45-70 wt% of starch, 8-16 wt% of plasticizer, 8-30 wt% of carrier, 3-12 wt% of compatilizer, 1-3 wt% of lubricant and 0.1-1 wt% of auxiliary agent.
3. The use of claim 2, wherein the starch concentrate composition comprises, based on the total weight of the starch concentrate composition:
50-65 wt% of starch, 10-14 wt% of plasticizer, 8-25 wt% of carrier, 6-10 wt% of compatilizer, 1-2 wt% of lubricant and 0.3-0.5 wt% of auxiliary agent.
4. Use according to any one of claims 1-3, wherein the starch is one or more of wheat starch, corn starch, tapioca starch and potato starch.
5. Use according to any one of claims 1 to 3, wherein the plasticizer is one or more of glycerol, glycerol monostearate, sorbitol, triethanolamine and urea.
6. Use according to any one of claims 1 to 3, wherein the carrier is a combination of one or more of LLDPE, EAA, EVA;
preferably, the LLDPE, EAA and EVA have a melt index in the range of 10-100g/10 min;
more preferably, the LLDPE, EAA, EVA have melt indices in the range of 20-50g/10 min.
7. Use according to any one of claims 1 to 3, wherein the compatibiliser is a grafted combination of one or more selected from LDPE and POE with one or more selected from maleic anhydride, itaconic anhydride, and substituted maleic anhydride.
8. Use according to claim 7, wherein the compatibilizer is a composition of LDPE-g-MA and POE-g-MA, wherein the weight ratio of LDPE-g-MA to POE-g-MA is 1: 0.5 to 2;
preferably, the grafting rate of the LDPE-g-MA is more than 0.5 percent;
preferably, the POE-g-MA grafting rate is more than 0.5 percent.
9. Use according to any one of claims 1 to 3, wherein the lubricant is one or more of PE wax, oxidized PE wax, calcium stearate and zinc stearate.
10. Use according to any one of claims 1 to 3, wherein the adjuvant is selected from antioxidants and antibacterial modifiers.
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| CN103205021A (en) * | 2012-01-11 | 2013-07-17 | 上海杰事杰新材料(集团)股份有限公司 | Thermoplastic and PBAT blend and preparation method thereof |
| CN104119647A (en) * | 2013-04-27 | 2014-10-29 | 上海杰事杰新材料(集团)股份有限公司 | High-starch full biodegradable composition and preparation method thereof |
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| CN103205021A (en) * | 2012-01-11 | 2013-07-17 | 上海杰事杰新材料(集团)股份有限公司 | Thermoplastic and PBAT blend and preparation method thereof |
| CN104119647A (en) * | 2013-04-27 | 2014-10-29 | 上海杰事杰新材料(集团)股份有限公司 | High-starch full biodegradable composition and preparation method thereof |
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