CN114644813A - Biodegradable plastic master batch produced by utilizing bio-based pBAt and preparation method thereof - Google Patents
Biodegradable plastic master batch produced by utilizing bio-based pBAt and preparation method thereof Download PDFInfo
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- 229920000704 biodegradable plastic Polymers 0.000 title claims abstract description 43
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011701 zinc Substances 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004952 Polyamide Substances 0.000 claims abstract description 14
- 229920000229 biodegradable polyester Polymers 0.000 claims abstract description 14
- 239000004622 biodegradable polyester Substances 0.000 claims abstract description 14
- SOROIESOUPGGFO-UHFFFAOYSA-N diazolidinylurea Chemical compound OCNC(=O)N(CO)C1N(CO)C(=O)N(CO)C1=O SOROIESOUPGGFO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229960001083 diazolidinylurea Drugs 0.000 claims abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 14
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 14
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 14
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 14
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 14
- 239000010451 perlite Substances 0.000 claims abstract description 14
- 235000019362 perlite Nutrition 0.000 claims abstract description 14
- 229920002647 polyamide Polymers 0.000 claims abstract description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 229920003023 plastic Polymers 0.000 claims abstract description 9
- 239000004033 plastic Substances 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 40
- 239000010902 straw Substances 0.000 claims description 40
- 238000005886 esterification reaction Methods 0.000 claims description 36
- 230000032050 esterification Effects 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 24
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000088 plastic resin Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 150000002148 esters Chemical group 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 238000006065 biodegradation reaction Methods 0.000 claims description 8
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 4
- 244000105624 Arachis hypogaea Species 0.000 claims description 4
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 4
- 235000018262 Arachis monticola Nutrition 0.000 claims description 4
- 239000004970 Chain extender Substances 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 240000008042 Zea mays Species 0.000 claims description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 235000005822 corn Nutrition 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 235000020232 peanut Nutrition 0.000 claims description 4
- 238000005453 pelletization Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 230000004580 weight loss Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- -1 titanium phosphorus compound Chemical class 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000018044 dehydration Effects 0.000 claims 1
- 239000003446 ligand Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 238000005809 transesterification reaction Methods 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 description 1
- JYLRDAXYHVFRPW-UHFFFAOYSA-N butane-1,1-diol;terephthalic acid Chemical compound CCCC(O)O.OC(=O)C1=CC=C(C(O)=O)C=C1 JYLRDAXYHVFRPW-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229920001896 polybutyrate Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- 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
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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
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2461/14—Modified phenol-aldehyde condensates
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2003/0893—Zinc
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- 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
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- C08K2201/011—Nanostructured additives
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- 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
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- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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Abstract
The application discloses a biodegradable plastic master batch produced by utilizing bio-based pBAt and a preparation method thereof, wherein the preparation method comprises the following steps: the degradable biological plastic master batch comprises, by weight, 40-60 parts of biodegradable polyester, 3-12 parts of modified phenolic resin, 4-12 parts of nano magnesium oxide, 2-4 parts of nano silicon powder, 3-8 parts of graphene, 2-6 parts of perlite, 1-4 parts of nano zinc, 2-4 parts of magnesium hydroxide whisker, 5-12 parts of antimony trioxide, 4-10 parts of polyamide wax micropowder, 2-8 parts of diazolidinyl urea and 3-5 parts of polyethylene glycol, and the weighing stage is as follows: 59 parts of biodegradable polyester, 5 parts of modified phenolic resin, 7 parts of nano magnesium oxide, 3 parts of nano silicon micropowder, 5 parts of graphene, 4 parts of perlite, 3 parts of nano zinc, 4 parts of magnesium hydroxide whisker, 8 parts of antimony trioxide, 4 parts of polyamide wax micropowder, 3 parts of diazolidinyl urea and 5 parts of polyethylene glycol are weighed according to parts by weight. The application provides a preparation method for producing degradable bioplastic master batch by utilizing bio-based pBAt.
Description
Technical Field
The application relates to a preparation method of a bioplastic master batch, in particular to a biodegradable bioplastic master batch produced by utilizing a bio-based pBAt and a preparation method thereof.
Background
Along with the continuous increase of the plastic consumption, waste plastics are increasing, especially the use of plastic products such as mulching films, disposable lunch boxes and the like causes serious pollution problems to the environment, in order to solve the pollution problems of plastic wastes to the environment, biodegradable plastics are widely researched, from the degradation mechanism, the currently researched biodegradable plastics are mainly divided into completely biodegradable plastics and incompletely biodegradable plastics, the completely biodegradable plastics are high molecular materials which are finally decomposed into inorganic substances such as water, carbon dioxide and the like, PBAT belongs to thermoplastic biodegradable plastics, is a copolymer of butanediol adipate and butanediol terephthalate, has the characteristics of PBA and PBT, has better ductility and elongation at break, and also has better heat resistance and impact performance; in addition, the biodegradable plastic has excellent biodegradability, and is one of the best degradable materials for active research and market application of biodegradable plastics.
At present, most plastic products can not be degraded after being discarded and exist for a long time, serious white pollution is caused by continuous accumulation, and with continuous increase of pollution and continuous enhancement of environmental awareness of people, the seeking of a plastic product which can meet the use requirement of people and the environmental requirement is more and more urgent and arouses the wide interest of researchers. Therefore, the method for producing the degradable bioplastic master batch by utilizing the bio-base pBAt and the preparation method thereof are provided aiming at the problems.
Disclosure of Invention
A biodegradable plastic master batch produced by utilizing bio-based pBAt and a preparation method thereof, wherein the biodegradable plastic master batch comprises, by weight, 40-60 parts of biodegradable polyester, 3-12 parts of modified phenolic resin, 4-12 parts of nano magnesium oxide, 2-4 parts of nano silicon micropowder, 3-8 parts of graphene, 2-6 parts of perlite, 1-4 parts of nano zinc, 2-4 parts of magnesium hydroxide whisker, 5-12 parts of antimony trioxide, 4-10 parts of polyamide wax micropowder, 2-8 parts of diazolidinyl urea and 3-5 parts of polyethylene glycol;
further, a preparation method for producing the degradable bioplastic master batch by utilizing the bio-based pBAt to obtain the degradable bioplastic master batch comprises the following steps:
(1) a weighing stage: weighing 59 parts of biodegradable polyester, 5 parts of modified phenolic resin, 7 parts of nano magnesium oxide, 3 parts of nano silicon micropowder, 5 parts of graphene, 4 parts of perlite, 3 parts of nano zinc, 4 parts of magnesium hydroxide whisker, 8 parts of antimony trioxide, 4 parts of polyamide wax micropowder, 3 parts of diazolidinyl urea and 5 parts of polyethylene glycol according to parts by weight, and taking out certain components of adipic acid and 1, 4-butanediol;
(2) and (3) mixing stage: mixing nano magnesium oxide, nano silicon micropowder, graphene, perlite, nano zinc, magnesium hydroxide whisker and antimony trioxide, adding the mixture into a grinder for grinding for 10-16 min to obtain a mixture A, adding polyamide wax micropowder and diazolidinyl urea into the mixture A, mixing, adding a small amount of medical alcohol, and fully stirring at normal temperature to obtain a mixture B; adding the biodegradable polyester into the mixture B, mixing, and then adding into a mixing roll for mixing, wherein the mixing temperature is 180-210 ℃, and the mixing time is 20-40 min, so as to obtain a mixture C;
(3) an esterification stage: respectively adding adipic acid and 1, 4-butanediol into a polycondensation reaction kettle according to a certain proportion, starting heating, adding a proper amount of chain extender polyalcohol after uniformly stirring, and continuously heating to perform normal pressure esterification dehydration reaction;
(4) and (3) ester exchange stage: after the esterification reaction is finished, adding dimethyl terephthalate or terephthalic acid and 1, 4-butanediol in a certain proportion, stirring for a moment, adding a titanium catalyst, heating to 200 ℃, and reacting in esterification, ester exchange and esterification stages to obtain a byproduct;
(5) a melt polycondensation stage: after the ester exchange/esterification stage reaction is complete, adding a titanium catalyst, a zinc catalyst and a stabilizer, heating to 235-plus 245 ℃ for polycondensation reaction, slowly pumping to high vacuum, controlling the vacuum to be 100-plus 1000Pa and 100Pa, and cooling and pelletizing to obtain pBAt with different molecular weights by controlling the discharging torque;
(6) and (3) drying and stirring stage: then drying the pBAt with different molecular weights in the step (5), and mixing the dried pBAt and the modifier in a closed high-speed stirrer for 5-10 minutes to obtain a main material;
(7) a melting stage: adjusting the weight loss feeder parameters according to the mixture ratio, respectively adding the mixture C obtained in the step (2) and the main material and the auxiliary agent in the step (6) into a screw extruder in proportion to be melted and blended at the mixing temperature of 130-160 ℃,
(8) and (3) mixing: mixing common plastic resin, an oxidative degradation additive and a biodegradation auxiliary agent, and then adding the hydroxyl-removed modified straw powder to obtain a mixture D; the mass ratio of the common plastic resin to the hydroxyl-removed modified straw powder is (15-50): (50-85);
(9) an extrusion stage: and mixing and extruding the mixture D to obtain the degradable bioplastic master batch.
Further, in the step (3), the temperature of the normal pressure esterification dehydration reaction is maintained at 130-150 ℃.
Further, in the step (3), the esterification and dehydration reaction is carried out until the water yield reaches 85% of the theoretical value, and the acid value is measured at the same time.
Further, in the step (3), the temperature is raised to 200 ℃, and a slow temperature raising mode is adopted to perform normal pressure ester exchange and esterification reaction for removing methanol and water.
Further, the reaction in the step (4) achieves water and methanol to be discharged until no product is distilled off.
Further, the melted materials in the step (7) are conveyed by a screw and extruded for granulation.
Further, the mass of the biodegradation auxiliary agent in the step (8) accounts for 1-10% of the total mass of the common plastic resin and the dehydroxy modified straw powder.
Further, the mass of the oxidative degradation additive in the step (8) accounts for 1% -30% of the total mass of the common plastic resin and the hydroxyl-removed modified straw powder, and the modified straw powder in the step (6) is selected from one or more of peanut straw powder, rice straw powder, corn straw powder, rape straw powder and cotton straw powder.
The beneficial effect of this application is: the application provides a biodegradable plastic master batch produced by utilizing bio-based pBAt and a preparation method thereof.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is a flow chart of the preparation method of the present application.
Detailed Description
In order to make the technical solutions better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only partial embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be noted that the terms "first," "second," and the like in the description and claims of this application and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It should be understood that the data so used may be interchanged under appropriate circumstances such that embodiments of the application described herein may be used. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
In the present application, the terms "upper", "lower", "left", "right", "front", "rear", "top", "bottom", "inner", "outer", "middle", "vertical", "horizontal", "lateral", "longitudinal", and the like indicate an orientation or positional relationship based on the orientation or positional relationship shown in the drawings. These terms are used primarily to better describe the present application and its embodiments, and are not used to limit the indicated devices, elements or components to a particular orientation or to be constructed and operated in a particular orientation.
Moreover, some of the above terms may be used to indicate other meanings besides the orientation or positional relationship, for example, the term "on" may also be used to indicate some kind of attachment or connection relationship in some cases. The specific meaning of these terms in this application will be understood by those of ordinary skill in the art as appropriate.
Furthermore, the terms "mounted," "disposed," "provided," "connected," and "sleeved" are to be construed broadly. For example, it may be a fixed connection, a removable connection, or a unitary construction; can be a mechanical connection, or an electrical connection; may be directly connected, or indirectly connected through intervening media, or may be in internal communication between two devices, elements or components. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art as appropriate.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.
The first embodiment is as follows:
a biodegradable plastic master batch produced by utilizing bio-based pBAt and a preparation method thereof, wherein the biodegradable plastic master batch comprises, by weight, 40-60 parts of biodegradable polyester, 3-12 parts of modified phenolic resin, 4-12 parts of nano magnesium oxide, 2-4 parts of nano silicon micropowder, 3-8 parts of graphene, 2-6 parts of perlite, 1-4 parts of nano zinc, 2-4 parts of magnesium hydroxide whisker, 5-12 parts of antimony trioxide, 4-10 parts of polyamide wax micropowder, 2-8 parts of diazolidinyl urea and 3-5 parts of polyethylene glycol;
a preparation method for producing degradable bioplastic master batch by utilizing bio-based pBAt to obtain the degradable bioplastic master batch comprises the following steps:
(1) a weighing stage: weighing 59 parts of biodegradable polyester, 5 parts of modified phenolic resin, 7 parts of nano magnesium oxide, 3 parts of nano silicon micropowder, 5 parts of graphene, 4 parts of perlite, 3 parts of nano zinc, 4 parts of magnesium hydroxide whisker, 8 parts of antimony trioxide, 4 parts of polyamide wax micropowder, 3 parts of diazolidinyl urea and 5 parts of polyethylene glycol according to parts by weight, and taking out certain components of adipic acid and 1, 4-butanediol;
(2) and (3) mixing: mixing nano magnesium oxide, nano silicon micropowder, graphene, perlite, nano zinc, magnesium hydroxide whisker and antimony trioxide, adding the mixture into a grinder for grinding for 10-16 min to obtain a mixture A, adding polyamide wax micropowder and diazolidinyl urea into the mixture A, mixing, adding a small amount of medical alcohol, and fully stirring at normal temperature to obtain a mixture B; adding the biodegradable polyester into the mixture B, mixing, and then adding into a mixing roll for mixing, wherein the mixing temperature is 180-210 ℃, and the mixing time is 20-40 min, so as to obtain a mixture C;
(3) an esterification stage: respectively adding adipic acid and 1, 4-butanediol into a polycondensation reaction kettle according to a certain proportion, starting heating, adding a proper amount of chain extender polyalcohol after uniformly stirring, and continuously heating to perform normal pressure esterification dehydration reaction;
(4) and (3) ester exchange stage: after the esterification reaction is finished, adding dimethyl terephthalate or terephthalic acid and 1, 4-butanediol in a certain proportion, stirring for a moment, adding a titanium catalyst, heating to 200 ℃, and reacting in esterification, ester exchange and esterification stages to obtain a byproduct;
(5) a melt polycondensation stage: after the ester exchange/esterification stage reaction is complete, adding a titanium catalyst, a zinc catalyst and a stabilizer, heating to 235-plus 245 ℃ for polycondensation reaction, slowly pumping to high vacuum, controlling the vacuum to be 100-plus 1000Pa and 100Pa, and cooling and pelletizing to obtain pBAt with different molecular weights by controlling the discharging torque;
(6) and (3) drying and stirring stage: then drying the pBAt with different molecular weights in the step (5), and mixing the dried pBAt and the modifier in a closed high-speed stirrer for 5-10 minutes to obtain a main material;
(7) a melting stage: adjusting the weight loss feeder parameters according to the mixture ratio, respectively adding the mixture C obtained in the step (2) and the main material and the auxiliary agent in the step (6) into a screw extruder in proportion to be melted and blended at the mixing temperature of 130-160 ℃,
(8) and (3) mixing: mixing common plastic resin, an oxidative degradation additive and a biodegradation auxiliary agent, and then adding the hydroxyl-removed modified straw powder to obtain a mixture D; the mass ratio of the common plastic resin to the dehydroxy modified straw powder is (15-50): (50-85);
(9) an extrusion stage: and mixing and extruding the mixture D to obtain the degradable bioplastic master batch.
Further, the temperature of the normal pressure esterification dehydration reaction in the step (3) is maintained at 130-150 ℃.
Further, in the step (3), the esterification and dehydration reaction is carried out until the water yield reaches 85% of the theoretical value, and the acid value is measured at the same time.
Further, in the step (3), the temperature is raised to 200 ℃, and a slow temperature raising mode is adopted to perform normal pressure ester exchange and esterification reaction for removing methanol and water.
Further, the reaction in the step (4) reaches water and methanol until no product is distilled off.
Further, the melted material in the step (7) is conveyed by a screw and extruded for granulation.
Further, the mass of the biodegradation auxiliary agent in the step (8) accounts for 5% of the total mass of the common plastic resin and the dehydroxy modified straw powder.
Further, the mass of the oxidative degradation additive in the step (8) accounts for 15% of the total mass of the common plastic resin and the hydroxyl-removed modified straw powder, and the modified straw powder in the step (6) is selected from one or more of peanut straw powder, rice straw powder, corn straw powder, rape straw powder and cotton straw powder.
The method is suitable for a preparation method for producing the degradable bioplastic master batch by utilizing the bio-based pBAt.
Example two:
a biodegradable plastic master batch produced by utilizing bio-based pBAt and a preparation method thereof, wherein the biodegradable plastic master batch comprises, by weight, 40-60 parts of biodegradable polyester, 3-12 parts of modified phenolic resin, 4-12 parts of nano magnesium oxide, 2-4 parts of nano silicon micropowder, 3-8 parts of graphene, 2-6 parts of perlite, 1-4 parts of nano zinc, 2-4 parts of magnesium hydroxide whisker, 5-12 parts of antimony trioxide, 4-10 parts of polyamide wax micropowder, 2-8 parts of diazolidinyl urea and 3-5 parts of polyethylene glycol;
a preparation method for producing degradable bioplastic master batch by utilizing bio-based pBAt comprises the following steps:
(1) a weighing stage: weighing 59 parts of biodegradable polyester, 5 parts of modified phenolic resin, 7 parts of nano magnesium oxide, 3 parts of nano silicon micropowder, 5 parts of graphene, 4 parts of perlite, 3 parts of nano zinc, 4 parts of magnesium hydroxide whisker, 8 parts of antimony trioxide, 4 parts of polyamide wax micropowder, 3 parts of diazolidinyl urea and 5 parts of polyethylene glycol according to parts by weight, and taking out certain components of adipic acid and 1, 4-butanediol;
(2) and (3) mixing: mixing nano magnesium oxide, nano silicon micropowder, graphene, perlite, nano zinc, magnesium hydroxide whisker and antimony trioxide, adding the mixture into a grinder for grinding for 10-16 min to obtain a mixture A, adding polyamide wax micropowder and diazolidinyl urea into the mixture A, mixing, adding a small amount of medical alcohol, and fully stirring at normal temperature to obtain a mixture B; adding the biodegradable polyester into the mixture B, mixing, and then adding into a mixing roll for mixing, wherein the mixing temperature is 180-210 ℃, and the mixing time is 20-40 min, so as to obtain a mixture C;
(3) an esterification stage: respectively adding adipic acid and 1, 4-butanediol into a polycondensation reaction kettle according to a certain proportion, starting heating, adding a proper amount of chain extender polyalcohol after uniformly stirring, and continuously heating to carry out normal-pressure esterification dehydration reaction;
(4) and (3) ester exchange stage: after the esterification reaction is finished, adding dimethyl terephthalate or terephthalic acid and 1, 4-butanediol in a certain proportion, stirring for a moment, adding a titanium catalyst, heating to 200 ℃, and reacting in esterification, ester exchange and esterification stages to obtain a byproduct;
(5) a melt polycondensation stage: after the ester exchange/esterification stage reaction is complete, adding a titanium catalyst, a zinc catalyst and a stabilizer, heating to 235-plus 245 ℃ for polycondensation reaction, slowly pumping to high vacuum, controlling the vacuum to be 100-plus 1000Pa and 100Pa, and cooling and pelletizing to obtain pBAt with different molecular weights by controlling the discharging torque;
(6) and (3) drying and stirring stage: then drying the pBAt with different molecular weights in the step (5), and mixing the dried pBAt and the modifier in a closed high-speed stirrer for 5-10 minutes to obtain a main material;
(7) a melting stage: adjusting the weight loss feeder parameters according to the mixture ratio, respectively adding the mixture C obtained in the step (2) and the main material and the auxiliary agent in the step (6) into a screw extruder in proportion to be melted and blended at the mixing temperature of 130-160 ℃,
(8) and (3) mixing: mixing common plastic resin, an oxidative degradation additive and a biodegradation auxiliary agent, and then adding the hydroxyl-removed modified straw powder to obtain a mixture D; the mass ratio of the common plastic resin to the dehydroxy modified straw powder is (15-50): (50-85);
(9) an extrusion stage: and mixing and extruding the mixture D to obtain the degradable bioplastic master batch.
Further, the temperature of the normal pressure esterification dehydration reaction in the step (3) is maintained at 130-150 ℃.
Further, in the step (3), the esterification and dehydration reaction is carried out until the water yield reaches 85% of the theoretical value, and the acid value is measured at the same time.
Further, in the step (3), the temperature is raised to 200 ℃, and a slow temperature raising mode is adopted to perform normal pressure ester exchange and esterification reaction for removing methanol and water.
Further, the reaction in the step (4) reaches water and methanol until no product is distilled off.
Further, the melted materials in the step (7) are conveyed by a screw and extruded for granulation.
Further, the mass of the biodegradation auxiliary agent in the step (8) accounts for 10% of the total mass of the common plastic resin and the dehydroxy modified straw powder.
Further, the mass of the oxidative degradation additive in the step (8) accounts for 30% of the total mass of the common plastic resin and the hydroxyl-removed modified straw powder, and the modified straw powder in the step (6) is selected from one or more of peanut straw powder, rice straw powder, corn straw powder, rape straw powder and cotton straw powder.
The method is suitable for preparing the degradable bioplastic master batch by utilizing the bio-based pBAt.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A method for producing degradable bioplastic master batch by utilizing bio-based pBAt and a preparation method thereof are characterized in that: the degradable bioplastic master batch comprises, by weight, 40-60 parts of biodegradable polyester, 3-12 parts of modified phenolic resin, 4-12 parts of nano magnesium oxide, 2-4 parts of nano silicon micropowder, 3-8 parts of graphene, 2-6 parts of perlite, 1-4 parts of nano zinc, 2-4 parts of magnesium hydroxide whisker, 5-12 parts of antimony trioxide, 4-10 parts of polyamide wax micropowder, 2-8 parts of diazolidinyl urea and 3-5 parts of polyethylene glycol.
2. The method for preparing the master batch of the degradable biological plastic by utilizing the pBAt of the bio-base to produce the master batch of the degradable biological plastic according to the claim 1, which is characterized in that:
(1) a weighing stage: weighing 59 parts of biodegradable polyester, 5 parts of modified phenolic resin, 7 parts of nano magnesium oxide, 3 parts of nano silicon micropowder, 5 parts of graphene, 4 parts of perlite, 3 parts of nano zinc, 4 parts of magnesium hydroxide whisker, 8 parts of antimony trioxide, 4 parts of polyamide wax micropowder, 3 parts of diazolidinyl urea and 5 parts of polyethylene glycol according to parts by weight, and taking out certain components of adipic acid and 1, 4-butanediol;
(2) and (3) mixing stage: mixing nano magnesium oxide, nano silicon micropowder, graphene, perlite, nano zinc, magnesium hydroxide whisker and antimony trioxide, adding the mixture into a grinder for grinding for 10-16 min to obtain a mixture A, adding polyamide wax micropowder and diazolidinyl urea into the mixture A, mixing, adding a small amount of medical alcohol, and fully stirring at normal temperature to obtain a mixture B; adding biodegradable polyester into the mixture B, mixing and adding into a mixing roll for mixing at the mixing temperature of 180-210 ℃ for 20-40 min to obtain a mixture C;
(3) an esterification stage: respectively adding adipic acid and 1, 4-butanediol into a polycondensation reaction kettle according to a certain proportion, starting heating, adding a proper amount of chain extender polyalcohol after uniformly stirring, and continuously heating to perform normal pressure esterification dehydration reaction;
(4) and (3) ester exchange stage: after the esterification reaction is finished, adding dimethyl terephthalate or terephthalic acid and 1, 4-butanediol in a certain proportion, stirring for a moment, adding a titanium catalyst, heating to 200 ℃, and reacting in esterification, ester exchange and esterification stages to obtain a byproduct;
(5) a melt polycondensation stage: after the ester exchange/esterification stage reaction is complete, adding a titanium catalyst, a zinc catalyst and a stabilizer, heating to 235-plus 245 ℃ for polycondensation reaction, slowly pumping to high vacuum, controlling the vacuum to be 100-plus 1000Pa and 100Pa, and cooling and pelletizing to obtain pBAt with different molecular weights by controlling the discharging torque;
(6) and (3) drying and stirring stage: then drying the pBAt with different molecular weights in the step (5), and mixing the dried pBAt and the modifier in a closed high-speed stirrer for 5-10 minutes to obtain a main material;
(7) a melting stage: adjusting the weight loss feeder parameters according to the mixture ratio, respectively adding the mixture C obtained in the step (2) and the main material and the auxiliary agent in the step (6) into a screw extruder according to the proportion, simultaneously melting and blending, wherein the mixing temperature is 130-160 ℃,
(8) and (3) mixing: mixing common plastic resin, an oxidative degradation additive and a biodegradation auxiliary agent, and then adding the hydroxyl-removed modified straw powder to obtain a mixture D; the mass ratio of the common plastic resin to the dehydroxy modified straw powder is (15-50): (50-85);
(9) an extrusion stage: and mixing and extruding the mixture D to obtain the degradable bioplastic master batch.
3. The preparation method of the degradable bioplastic masterbatch of claim 2, wherein the preparation method comprises the following steps: the temperature of the normal pressure esterification dehydration reaction in the step (3) is kept at 130-150 ℃.
4. The preparation method of the degradable bioplastic masterbatch of claim 2, wherein the preparation method comprises the following steps: in the step (3), esterification and dehydration are carried out until the water yield reaches 85% of a theoretical value, and the acid value is measured at the same time.
5. The method for preparing biodegradable bioplastic masterbatch of claim 2, wherein in the step (3), the temperature is raised to 200 ℃ and the reaction of removing methanol and water by normal pressure transesterification and esterification is performed by using a slow temperature raising method.
6. The method for preparing the biodegradable plastic masterbatch according to claim 2, wherein the method comprises the following steps: in the step (4), the reaction reaches water and methanol until no product is distilled off.
7. The preparation method of the degradable bioplastic masterbatch of claim 2, wherein the preparation method comprises the following steps: the titanium catalyst in the step (4) is a titanium phosphorus compound, and the titanium phosphorus compound is a compound which takes titanium as a central atom and a phosphorus compound as a ligand.
8. The preparation method of the degradable bioplastic masterbatch of claim 2, wherein the preparation method comprises the following steps: and (4) conveying the melted materials in the step (7) through a screw rod, and extruding and granulating the materials.
9. The method for preparing the biodegradable plastic masterbatch according to claim 2, wherein the method comprises the following steps: the mass of the biodegradation auxiliary agent in the step (8) accounts for 1-10% of the total mass of the common plastic resin and the dehydroxy modified straw powder.
10. The preparation method of the degradable bioplastic masterbatch of claim 2, wherein the preparation method comprises the following steps: the mass of the oxidative degradation additive in the step (8) accounts for 1-30% of the total mass of the common plastic resin and the hydroxyl-removed modified straw powder, and the modified straw powder in the step (6) is selected from one or more of peanut straw powder, rice straw powder, corn straw powder, rape straw powder and cotton straw powder.
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| CN108892930A (en) * | 2018-06-08 | 2018-11-27 | 吕龙芳 | A kind of biodegradable modified plastic agglomerate and preparation method thereof |
| CN108948684A (en) * | 2018-06-05 | 2018-12-07 | 张英海 | A kind of environmental protection PBT engineering plastics and preparation method thereof |
| CN111875937A (en) * | 2020-07-23 | 2020-11-03 | 宁夏中原塑业科技有限公司 | Function-adjusting master batch for biodegradation and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108948684A (en) * | 2018-06-05 | 2018-12-07 | 张英海 | A kind of environmental protection PBT engineering plastics and preparation method thereof |
| CN108892930A (en) * | 2018-06-08 | 2018-11-27 | 吕龙芳 | A kind of biodegradable modified plastic agglomerate and preparation method thereof |
| CN111875937A (en) * | 2020-07-23 | 2020-11-03 | 宁夏中原塑业科技有限公司 | Function-adjusting master batch for biodegradation and preparation method thereof |
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