CN117003945A - Vinyl acetate grafted starch, preparation method and application thereof, starch/PBAT composite material and preparation method thereof - Google Patents
Vinyl acetate grafted starch, preparation method and application thereof, starch/PBAT composite material and preparation method thereof Download PDFInfo
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- CN117003945A CN117003945A CN202311013885.4A CN202311013885A CN117003945A CN 117003945 A CN117003945 A CN 117003945A CN 202311013885 A CN202311013885 A CN 202311013885A CN 117003945 A CN117003945 A CN 117003945A
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- 229920002472 Starch Polymers 0.000 title claims abstract description 183
- 235000019698 starch Nutrition 0.000 title claims abstract description 183
- 239000008107 starch Substances 0.000 title claims abstract description 183
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920001896 polybutyrate Polymers 0.000 title claims abstract 11
- 239000003999 initiator Substances 0.000 claims abstract description 34
- 230000004048 modification Effects 0.000 claims abstract description 23
- 238000012986 modification Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 32
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical group [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 5
- 235000013305 food Nutrition 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 16
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 235000011187 glycerol Nutrition 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229920002261 Corn starch Polymers 0.000 description 5
- 239000008120 corn starch Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- -1 Polybutylene terephthalate-adipate Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- MKRNVBXERAPZOP-UHFFFAOYSA-N Starch acetate Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OC(C)=O)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 MKRNVBXERAPZOP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012899 standard injection Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention provides vinyl acetate grafted starch, a preparation method and application thereof, a starch/PBAT composite material and a preparation method thereof, and relates to the technical field of high polymer materials. The invention mixes starch with water for gelatinization to obtain gelatinized starch; and mixing the gelatinized starch, vinyl acetate and an initiator for grafting modification to obtain the vinyl acetate grafted starch. The invention takes starch as raw material, water as solvent, vinyl acetate as grafting monomer, and prepares grafted starch under the action of initiator. The vinyl acetate grafted starch prepared by the method is used as a compatibilizer to compatibilize a starch/PBAT system, so that the complete compatibility of the starch and the PBAT can be realized; compared with other compatilizers, the vinyl acetate grafted starch prepared by the invention has low price and can be fully biodegradable, so that the starch/PBAT composite material is further separated from full starch plastic, and is expected to enter the field of food packaging.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to vinyl acetate grafted starch, a preparation method and application thereof, a starch/PBAT composite material and a preparation method thereof.
Background
The traditional petroleum-based plastic is difficult to degrade and has serious influence on the environment, and the development and research of the environment-friendly biodegradable plastic become one of the important directions of future development of the plastic industry. Polybutylene terephthalate-adipate (PBAT) is a thermoplastic biodegradable material with excellent performance, has high elongation and good toughness, and can be applied to the fields of degradable film bags, mulching films and the like. But the PBAT has higher price and is difficult to popularize and apply on a large scale. The starch is taken as a natural macromolecule, the source is wide, the price is low, and the starch/PBAT composite material prepared by blending the PBAT and the starch can reduce the material cost on the basis of ensuring the degradability, thereby having good development prospect.
However, starch has poor compatibility with PBAT materials, and a compatibilizer is required to improve the compatibility of the starch and the PBAT material. The addition of a suitable compatibilizer can not only further improve the performance of the starch/PBAT composite material, but also add more starch without affecting the comprehensive performance of the composite material, thereby further reducing the cost. Commonly used compatibilizers are mainly tributyl citrate (TBC), triphenyl phosphite (TPPI), soluble Polyesters (PVEs). However, the compatibilizing effect of these compatibilizers remains to be improved, and the starch cannot be fully compatible with PBAT; and the price is higher, and the production cost is increased.
Disclosure of Invention
In view of the above, the invention aims to provide vinyl acetate grafted starch, a preparation method and application thereof, a starch/PBAT composite material and a preparation method thereof. The vinyl acetate grafted starch prepared by the invention can be used as a compatibilizer to realize the complete compatibility of the starch and PBAT, and the cost is low.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of vinyl acetate grafted starch, which comprises the following steps:
mixing starch with water for gelatinization to obtain gelatinized starch;
and mixing the gelatinized starch, vinyl acetate and an initiator for grafting modification to obtain the vinyl acetate grafted starch.
Preferably, the gelatinization temperature is 80-120 ℃.
Preferably, the mass ratio of the starch to the vinyl acetate is (0.8-1.2): (1.8-2.2).
Preferably, the initiator is ceric ammonium nitrate, and the mass of the initiator is 2.5-3.5% of the mass of the starch.
Preferably, the specific operation of the grafting modification comprises the following steps:
sequentially adding part of vinyl acetate and part of initiator into the gelatinized starch, and then simultaneously dripping the rest of vinyl acetate and the rest of initiator into the obtained mixture;
the partial vinyl acetate is 1/3 of the total mass of the vinyl acetate, and the partial initiator is 1/3 of the total mass of the initiator; the residual vinyl acetate had a drop rate of 3 s/drop and the residual initiator had a drop rate of 20 s/drop.
Preferably, the temperature of the grafting modification is 40-60 ℃ and the time is 3-5 h, and the time of the grafting modification is calculated from the completion of the addition of the part of vinyl acetate; the grafting modification is carried out in a nitrogen atmosphere.
The invention provides the vinyl acetate grafted starch prepared by the preparation method.
The invention provides application of the vinyl acetate grafted starch in the preparation of starch/PBAT composite material as a compatibilizer.
The invention provides a starch/PBAT composite material, which comprises the following preparation raw materials in parts by weight: 1 part of starch, 0.25 to 0.5 part of glycerol, 0.3 to 0.6 part of compatibilizer and 0.8 to 1.2 parts of PBAT; the compatibilizer is the vinyl acetate grafted starch in the technical scheme.
The invention provides a preparation method of the starch/PBAT composite material, which comprises the following steps:
and mixing the starch, the glycerol and the compatibilizer for preplasticizing, and carrying out twin-screw extrusion processing on the obtained mixture and the PBAT to obtain the starch/PBAT composite material.
The invention provides a preparation method of vinyl acetate grafted starch, which comprises the following steps: mixing starch with water for gelatinization to obtain gelatinized starch; and mixing the gelatinized starch, vinyl acetate and an initiator for grafting modification to obtain the vinyl acetate grafted starch. The invention takes starch as raw material, water as solvent, vinyl acetate as grafting monomer, and prepares grafted starch under the action of initiator. The vinyl acetate grafted starch prepared by the method is used as a compatibilizer to compatibilize a starch/PBAT system, so that the compatibility of the starch and the PBAT can be obviously improved, and the complete compatibility of the starch and the PBAT can be realized; compared with other compatilizers, the vinyl acetate grafted starch prepared by the invention has low price and can be fully biodegradable, so that the starch/PBAT composite material is further separated from full starch plastic, and is expected to enter the field of food packaging.
Drawings
FIG. 1 is an electron microscope image of raw corn starch in example 1;
FIG. 2 is an electron micrograph of a vinyl acetate grafted starch of example 1;
FIG. 3 is a thermogravimetric plot of raw corn starch and vinyl acetate grafted starch of example 1;
FIG. 4 is a cross-sectional electron micrograph of the starch/PBAT composite with different compatibilizers of example 2 and comparative examples 1-4. In FIG. 4, a-e correspond to example 1 (no compatibilizer), comparative example 2 (TBC), comparative example 3 (TPPI), comparative example 4 (PVE), example 2 (vinyl acetate grafted starch) in that order.
Detailed Description
The invention provides a preparation method of vinyl acetate grafted starch, which comprises the following steps:
mixing starch with water for gelatinization to obtain gelatinized starch;
and mixing the gelatinized starch, vinyl acetate and an initiator for grafting modification to obtain the vinyl acetate grafted starch.
The invention mixes starch with water to gelatinize, and the gelatinized starch is obtained. The starch of the present invention is not particularly limited, and starch well known to those skilled in the art may be used. In the present invention, the water is preferably distilled water; the gelatinization temperature is preferably 80 to 120 ℃, more preferably 95 ℃, the gelatinization temperature is preferably realized in the form of a water bath, and the gelatinization time is preferably more than 30min, particularly based on complete gelatinization. In the invention, water is preferably added into the starch to prepare emulsion with the solid content of 33 weight percent, and then the emulsion is heated to 80-120 ℃ for gelatinization; the gelatinization is preferably carried out under continuous stirring.
After the gelatinized starch is obtained, the gelatinized starch, the vinyl acetate and the initiator are mixed for grafting modification, and the vinyl acetate grafted starch is obtained. In the invention, the mass ratio of the starch to the vinyl acetate is preferably (0.8-1.2): (1.8-2.2), more preferably 1:2; the initiator is preferably ceric ammonium nitrate, the mass of the initiator is preferably 2.5-3.5% of the mass of starch, more preferably 3%, and the addition of the initiator can improve the grafting rate and efficiency.
In the present invention, the specific operation of the graft modification preferably comprises the steps of:
sequentially adding part of vinyl acetate and part of initiator into the gelatinized starch, and then simultaneously dripping the rest of vinyl acetate and the rest of initiator into the obtained mixture;
the partial vinyl acetate is 1/3 of the total mass of the vinyl acetate, and the partial initiator is 1/3 of the total mass of the initiator; the residual vinyl acetate had a drop rate of 3 s/drop and the residual initiator had a drop rate of 20 s/drop.
In the present invention, the temperature of the graft modification is preferably 40 to 60 ℃, more preferably 50 ℃, and the time is preferably 3 to 5 hours, the time of the graft modification being calculated from the completion of the addition of the part of vinyl acetate (the time of the graft modification does not include the time of the addition of vinyl acetate and the initiator). In the embodiment of the invention, the time of grafting modification is preferably 4 hours, specifically, after adding part of vinyl acetate, stirring for 10 minutes, adding part of initiator, and reacting for 50 minutes; and then, simultaneously dropwise adding the residual vinyl acetate and the residual initiator, and continuing to react for 3 hours after the completion of dropwise adding. Because the vinyl acetate is volatile, the adoption of the mixing mode is favorable for the vinyl acetate to fully participate in the reaction.
In the invention, the grafting modification is preferably carried out in a nitrogen atmosphere, and volatile liquid is recovered by condensation through a condensation pipe.
After the grafting modification, the invention preferably cools the obtained reaction material to room temperature, carries out alcohol precipitation, and then filters to obtain the vinyl acetate grafted starch. In the present invention, the alcohol reagent used for the alcohol precipitation is preferably ethanol.
The invention provides the vinyl acetate grafted starch prepared by the preparation method. The vinyl acetate grafted starch is obtained by modifying original starch, is homologous to the original starch, has good compatibilization effect, can be completely biodegraded, has no pollution to the environment, and is low in cost.
The invention provides application of the vinyl acetate grafted starch in the preparation of starch/PBAT composite material as a compatibilizer. The vinyl acetate grafted starch provided by the invention is used as a compatibilizer to compatibilize a starch/PBAT system, so that the compatibility of the starch and the PBAT can be obviously improved, and the complete compatibility of the starch and the PBAT can be realized; the vinyl acetate grafted starch provided by the invention can be completely degraded, so that the starch/PBAT composite material is further compared with the full starch plastic, and the starch/PBAT composite material is expected to enter the field of food packaging.
The invention provides a starch/PBAT composite material, which comprises the following preparation raw materials in parts by weight: 1 part of starch, 0.25 to 0.5 part of glycerol, 0.3 to 0.6 part of compatibilizer, and 0.8 to 1.2 parts of PBAT (polybutylene terephthalate-adipate); the compatibilizer is the vinyl acetate grafted starch in the technical scheme. In the present invention, the glycerin is preferably 0.4 part, the compatibilizer is preferably 0.4 part, and the PBAT is preferably 1 part.
In the present invention, the glycerol plasticizes the starch as a plasticizer.
The starch and the PBAT in the starch/PBAT composite material provided by the invention are completely compatible, and are a uniform starch-based bio-plastic system, and the starch/PBAT composite material has excellent mechanical properties, and the tensile strength can reach 28.6+/-1.5 MPa.
The invention provides a preparation method of the starch/PBAT composite material, which comprises the following steps:
and mixing the starch, the glycerol and the compatibilizer for preplasticizing, and carrying out twin-screw extrusion processing on the obtained mixture and the PBAT to obtain the starch/PBAT composite material.
In the present invention, the pre-plasticizing is preferably performed in a high-speed mixer, and the time for the pre-plasticizing is preferably 8 minutes or more. According to the invention, starch, glycerol and compatibilizer are fully mixed through the pre-plasticizing, so that the effect of uniform dispersion is achieved, and the next operation is facilitated.
In the invention, the twin-screw extruder adopted in the twin-screw extrusion processing is preferably provided with six temperature areas from one area to six areas in sequence, the temperature is 140 ℃, 155 ℃, 150 ℃, 140 ℃ and 140 ℃, and the rotating speed of the twin-screw extruder is preferably 280r/min.
For further explanation of the present invention, the following examples are provided to describe the vinyl acetate grafted starch and its preparation method and application and the starch/PBAT composite material and its preparation method in detail, but they should not be construed as limiting the scope of the invention.
Example 1
The preparation method of the vinyl acetate grafted starch comprises the following steps:
adding 30g of corn starch into distilled water to prepare emulsion with the solid content of 33wt%, introducing the emulsion into a 500mL five-necked bottle, heating to 95 ℃ in a water bath kettle, and continuously stirring to gelatinize the starch to obtain gelatinized starch;
cooling gelatinized starch to 50 ℃, protecting by full nitrogen filling, condensing by a full condensing tube to recover volatile liquid, adding part of vinyl acetate (the total adding amount of the vinyl acetate is 60g, 1/3 is added firstly), adding part of initiator ceric ammonium nitrate (the total adding amount of the ceric ammonium nitrate is 3% of the total mass of the starch, 1/3 is added firstly, ceric ammonium nitrate is dissolved in distilled water in advance), reacting for 50min, then adding the rest 2/3 of vinyl acetate at a speed of 3 s/drop by using a constant-pressure dropping funnel, simultaneously adding the rest 2/3 of ceric ammonium nitrate at a speed of 20 s/drop by using the constant-pressure dropping funnel (ensuring that the rest 2/3 of ceric ammonium nitrate is firstly dripped), and continuing reacting for 3h after all the ceric ammonium nitrate is dripped (namely, the total reacting time is 4 h). After the reaction is completed, cooling to room temperature, precipitating with ethanol, filtering and separating with a suction filter, taking out the filtrate, measuring the water content of the filtrate, and preserving for later use.
Example 2
A starch/PBAT composite material, which uses the vinyl acetate grafted starch prepared in the example 1 as a compatibilizer, and the raw materials are used in the amount: 1 part by mass of starch, 0.4 part by mass of glycerol, 0.4 part by mass of vinyl acetate grafted starch and 1 part by mass of PBAT, wherein the preparation method comprises the following steps:
starch, glycerol and vinyl acetate grafted starch are proportioned according to the mass ratio, pre-plasticizing processing is carried out by a high-speed mixer, PBAT is added, processing is carried out by a double-screw extruder (the double-screw extruder is provided with six temperature areas, the temperature is 140 ℃, 155 ℃, 150 ℃, 140 ℃ and 140 ℃ in sequence, and the rotating speed of the double-screw extruder is 280 r/min), and standard injection molding parts are processed by an injection molding machine after pelleting.
Comparative example 1
The vinyl acetate grafted starch was omitted and the remainder was the same as in example 2.
Comparative example 2
The vinyl acetate grafted starch of example 2 was replaced with TBC (tributyl citrate) and the remainder was the same as in example 2.
Comparative example 3
The vinyl acetate grafted starch of example 2 was replaced with TPPI (triphenyl phosphite) and the remainder was the same as example 2.
Comparative example 4
The vinyl acetate grafted starch of example 2 was replaced with PVEs (soluble polyester, supplied by Hubei Di Summit New Environment Biomass materials Co., ltd.) and the remainder was the same as in example 2.
FIGS. 1 and 2 are, in order, electron microscopy images of raw corn starch and vinyl acetate grafted starch in example 1. As can be seen from fig. 1 and 2, the starch has a smooth appearance profile without any modification, and after the esterification grafting treatment, the starch granules become irregular, and the damaged condition of the granule surface is characterized more and more seriously because the vinyl acetate molecules can enter the starch molecules.
FIG. 3 is a thermogravimetric plot of raw corn starch and vinyl acetate grafted starch of example 1. The weight loss process of vinyl acetate grafted starch is divided into two stages. The first stage is mainly because the combination of starch and water molecules is destroyed by temperature, the weight loss temperature of the vinyl acetate grafted starch in the first stage is about 120 ℃, the mass loss is 11.09%, and the mass of the starch is basically unchanged at the temperature of 130-253 ℃; the second stage is the main stage of starch weight loss, wherein starch is heated and decomposed, the quality is rapidly reduced, the quality loss is caused by molecular structure damage of starch and quality loss caused by air ashing, the stage can be regarded as judging the thermal stability of a sample, the quality loss of the vinyl acetate grafted starch is 75.48% in the stage, the initial temperature in the process of heating and decomposing is about 260 ℃, and the quality loss is fastest at 314.9 ℃.
FIG. 4 is a cross-sectional electron micrograph of the starch/PBAT composite with different compatibilizers of example 2 and comparative examples 1-4. In FIG. 4, a-e correspond to example 1 (no compatibilizer), comparative example 2 (TBC), comparative example 3 (TPPI), comparative example 4 (PVE), example 2 (vinyl acetate grafted starch) in that order. As can be seen by observing an electron microscope image of a composite material added with TBC and TPPI, the gelatinized starch and the PBAT have obvious demarcation lines, gaps are formed between the gelatinized starch and the PBAT, and a plurality of cavities are formed on a PBAT matrix, so that the gelatinized starch particles fall off from the PBAT matrix when the adhesion between the starch and the PBAT interface is poor and the gelatinized starch particles are brittle; many voids are formed on the material added with TPPI, the gelatinized starch is agglomerated, and compared with an electron microscope image without a compatibilizer, the gelatinized starch is agglomerated more seriously and the voids become more, which indicates that TBC and TPPI do not compatibilize the gelatinized starch and PBAT two-phase system, but have opposite effects. By observing the electron microscope image of the composite material added with PVE, the gelatinized starch and the PBAT are melted together, the boundary between the gelatinized starch and the PBAT is hardly seen, only a small amount of starch particles are seen, and no obvious large particle and particle agglomeration phenomenon exists, because the PVE plays a role of starch plasticizer, weakens intermolecular and intramolecular hydrogen bonding of starch, and plays a role of dispersing agent and lubricant in the composite material system, so that the gelatinized starch particles are dispersed more uniformly, and the PVE can effectively compatibilize the gelatinized starch and the PBAT. As can be seen from an electron microscope image of the composite material added with the vinyl acetate grafted starch, the vinyl acetate grafted starch is used as a compatibilizer, no starch particles are found at the whole interface, brittle fracture hills are uniformly distributed at the whole interface, and the fact that the raw starch and the grafted starch are fully fused with the PBAT is proved, so that the compatibility is good, and a uniform system is formed.
The tensile strength of the starch/PBAT composites with different compatibilizers added according to ISO 527-2 standard for example 2 and for comparative examples 1 to 4 is shown in Table 1:
TABLE 1 tensile Strength of starch/PBAT composite materials of example 2 and comparative examples 1-4
As can be seen from Table 1, the starch/PBAT composite material obtained by using the vinyl acetate grafted starch as a compatibilizer has excellent mechanical properties.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the vinyl acetate grafted starch is characterized by comprising the following steps of:
mixing starch with water for gelatinization to obtain gelatinized starch;
and mixing the gelatinized starch, vinyl acetate and an initiator for grafting modification to obtain the vinyl acetate grafted starch.
2. The method according to claim 1, wherein the gelatinization temperature is 80 to 120 ℃.
3. The preparation method according to claim 1, wherein the mass ratio of the starch to the vinyl acetate is (0.8-1.2): (1.8-2.2).
4. The preparation method according to claim 1, wherein the initiator is ceric ammonium nitrate, and the mass of the initiator is 2.5-3.5% of the mass of starch.
5. The preparation method according to claim 1, 3 or 4, wherein the specific operation of grafting modification comprises the following steps:
sequentially adding part of vinyl acetate and part of initiator into the gelatinized starch, and then simultaneously dripping the rest of vinyl acetate and the rest of initiator into the obtained mixture;
the partial vinyl acetate is 1/3 of the total mass of the vinyl acetate, and the partial initiator is 1/3 of the total mass of the initiator; the residual vinyl acetate had a drop rate of 3 s/drop and the residual initiator had a drop rate of 20 s/drop.
6. The method according to claim 5, wherein the temperature of the graft modification is 40 to 60 ℃ and the time is 3 to 5 hours, the time of the graft modification being calculated from the completion of the addition of the part of vinyl acetate; the grafting modification is carried out in a nitrogen atmosphere.
7. The vinyl acetate grafted starch prepared by the preparation method of any one of claims 1 to 6.
8. Use of the vinyl acetate grafted starch of claim 7 as a compatibilizer in the preparation of starch/PBAT composites.
9. The starch/PBAT composite material is characterized by comprising the following preparation raw materials in parts by weight: 1 part of starch, 0.25 to 0.5 part of glycerol, 0.3 to 0.6 part of compatibilizer and 0.8 to 1.2 parts of PBAT; the compatibilizer is the vinyl acetate grafted starch of claim 7.
10. The method for preparing the starch/PBAT composite material according to claim 9, which comprises the following steps:
and mixing the starch, the glycerol and the compatibilizer for preplasticizing, and carrying out twin-screw extrusion processing on the obtained mixture and the PBAT to obtain the starch/PBAT composite material.
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| US20050171249A1 (en) * | 2002-02-28 | 2005-08-04 | Ya-Jane Wang | Biodegradable materials from starch-grafted polymers |
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| US20050171249A1 (en) * | 2002-02-28 | 2005-08-04 | Ya-Jane Wang | Biodegradable materials from starch-grafted polymers |
| CN102690488A (en) * | 2012-06-07 | 2012-09-26 | 上海还原企业发展有限公司 | Degradable starch-based plastic |
| CN105524219A (en) * | 2014-09-28 | 2016-04-27 | 上海东升新材料有限公司 | Starch graft modification method, graft-modified starch and application of graft-modified starch in degradable plastics |
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