CN115433390A - Chain extender for degradable plastics and preparation method thereof - Google Patents
Chain extender for degradable plastics and preparation method thereof Download PDFInfo
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- CN115433390A CN115433390A CN202211234699.9A CN202211234699A CN115433390A CN 115433390 A CN115433390 A CN 115433390A CN 202211234699 A CN202211234699 A CN 202211234699A CN 115433390 A CN115433390 A CN 115433390A
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- chain extender
- degradable plastics
- isocyanate
- layered graphene
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- 239000004970 Chain extender Substances 0.000 title claims abstract description 67
- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 36
- 239000012948 isocyanate Substances 0.000 claims abstract description 29
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 18
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000006068 polycondensation reaction Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- -1 (adipic acid) 1,4-butanediol-diethylene glycol Chemical compound 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- FZWBABZIGXEXES-UHFFFAOYSA-N ethane-1,2-diol;hexanedioic acid Chemical compound OCCO.OC(=O)CCCCC(O)=O FZWBABZIGXEXES-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical group CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- PMDHMYFSRFZGIO-UHFFFAOYSA-N 1,4,7-trioxacyclotridecane-8,13-dione Chemical compound O=C1CCCCC(=O)OCCOCCO1 PMDHMYFSRFZGIO-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Substances OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 229940106012 diethylene glycol adipate Drugs 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920005586 poly(adipic acid) Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 abstract description 16
- 239000013078 crystal Substances 0.000 abstract description 15
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000969 carrier Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000002131 composite material Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000704 biodegradable plastic Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920001896 polybutyrate Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920008262 Thermoplastic starch Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003777 experimental drug Substances 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- FRXFBIWLAJRBQW-UHFFFAOYSA-N hexanedioic acid;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.OC(=O)CCCCC(O)=O FRXFBIWLAJRBQW-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000004628 starch-based polymer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/06—Polyurethanes from polyesters
Abstract
The invention provides a chain extender for degradable plastics and a preparation method thereof, and relates to the technical field of chain extenders. The chain extender for the degradable plastics comprises, by mass, 20-35 parts of isocyanate, 60-75 parts of organic compounds with hydroxyl groups, 0.05-0.1 part of catalysts, 10-15 parts of layered graphene carriers, 0.2-0.5 part of accelerators and 0.5-1 part of zinc stearate. The chain extender for the degradable plastics provided by the invention takes the layered graphene as a carrier, and the layered graphene is of a planar structure, and the surface of the layered graphene contains a large number of active groups, so that the graphene has good dispersibility, the isocyanate chain extender can be well dispersed in the degradable polyester, the local excess of isocyanate is avoided, and the problem of gel or crystal points of a product is solved.
Description
Technical Field
The invention relates to the technical field of chain extenders, in particular to a chain extender for degradable plastics and a preparation method thereof.
Background
The degradable plastic is a plastic which has various properties meeting the use requirements, has unchanged performance in the preservation period and can be degraded into substances harmless to the environment under the natural environment condition after being used. Various degradable plastics exist, including photodegradable plastics, biodegradable plastics, photo/oxidation/full biodegradation plastics, carbon dioxide-based biodegradable plastics, thermoplastic starch resin degradable plastics and the like. Biodegradable materials are one of the most effective ways to solve white pollution at present. For biodegradable plastics, the structure of the biodegradable plastic often contains reactive groups such as hydroxyl, carboxyl and the like, and molecular chain growth and crosslinking can be realized through a chain extender, so that the processing and application performance of products is improved, and the diversification of processing modes and application fields is realized.
The chain extender, also called chain extender, is a substance that can react with functional groups on the linear polymer chain to extend the molecular chain and increase the molecular weight. Is often used for improving the mechanical property and the processing property of products such as polyurethane, polyester and the like. The chain extenders used to date include mainly epoxy functionalized polymer chain extenders, maleic anhydride functionalized polymer chain extenders, isocyanate based chain extenders, oxazoline based chain extenders, and the like.
At present, the isocyanate chain extender is usually found to have good dispersibility in polyester and be easy to form gel or crystal points, which affects the effect of the degradable polyester plastic finished product.
Disclosure of Invention
In order to solve the problems that the isocyanate chain extender mentioned in the background art has good dispersibility in polyester and is easy to form gel or crystal points, and the effect of a degradable polyester plastic finished product is influenced, the chain extender for the degradable plastic provided by the invention takes the layered graphene as a carrier, and because the layered graphene is in a planar structure and contains a large number of active groups on the surface, the graphene has good dispersibility, the isocyanate chain extender can be well dispersed in the degradable polyester, the local excess of isocyanate is avoided, and the problem of gel or crystal points of the product is solved.
The chain extender for degradable plastics comprises, by mass, 20-35 parts of isocyanate, 60-75 parts of organic compound with hydroxyl, 0.05-0.1 part of catalyst, 10-15 parts of layered graphene carrier, 0.2-0.5 part of accelerator and 0.5-1 part of zinc stearate.
In carrying out the above embodiment, preferably, the isocyanate is one or more of toluene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate, and cyclohexanedimethyl diisocyanate.
In carrying out the above embodiment, preferably, the hydroxyl organic compound is one or more of poly (ethylene glycol adipate) glycol, poly (diethylene glycol adipate) glycol, poly (neopentyl glycol adipate) 1,4 butanediol glycol, poly (ethylene glycol adipate) glycol-diethylene glycol, or poly (adipic acid) 1,4-butanediol-diethylene glycol.
In carrying out the above embodiment, it is preferable that the hydroxyl group-containing organic compound has a number average molecular weight of 400 to 8000Dalton.
In carrying out the above embodiment, preferably, the catalyst is an amine catalyst.
In the implementation of the above embodiment, preferably, the weight ratio of the isocyanate to the layered graphene carrier is 3:1.
In carrying out the above embodiment, preferably, the accelerator is dimethylbenzylamine or monomethylimidazole.
On the other hand, the preparation method of the chain extender for degradable plastics comprises the following steps:
step one, mixing isocyanate, an organic compound with hydroxyl and a catalyst, and carrying out polycondensation reaction to obtain a polycondensate for later use;
step two, mixing the polycondensate obtained in the step one with a layered graphene carrier, adding an accelerant, stirring at high temperature and high pressure to ensure that the polycondensate and the layered graphene carrier are fully reacted, standing and cooling to obtain a polymer for later use;
and step three, uniformly mixing the polymer obtained in the step two and zinc stearate at a high speed at room temperature to obtain the chain extender.
In carrying out the above embodiment, the temperature of the polycondensation reaction in step one is preferably in the range of 60 to 120 ℃.
In the above embodiment, the conditions of high temperature and high pressure in the second step are preferably 150 to 200 ℃ and 4 to 5MPa.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the chain extender for the degradable plastic, the layered graphene is added, so that a composite product is obtained by taking a polycondensation product of isocyanate and an organic compound with hydroxyl as a carrier. The graphene surface contains a large number of active groups such as hydroxyl, carboxyl and ester groups, and the active groups enable the graphene oxide to have good dispersibility and reaction activity, improve the good dispersion of the isocyanate chain extender in the degradable polyester, avoid the local excess of isocyanate and solve the problem of product gel or crystal point. In addition, the addition of the layered graphene may improve the rigidity of the polyester resin.
2. The chain extender for degradable plastics further improves the dispersibility of the chain extender in the biological polyester by modifying the isocyanate with the hydroxyl organic compound. Meanwhile, the modified chain extender can control the reactivity of the isocyanate chain extender and hydroxyl in polyester more easily, and the production process is more stable and controllable.
3. The active group contained on the surface of the graphene added by the chain extender for the degradable plastic can react with the group on the polyester, so that the branching degree is further improved. In addition, zinc stearate is added, so that the ring opening reaction of an epoxy group on the graphene can be catalyzed, the chain extension temperature is reduced, and the utilization rate of the epoxy group is remarkably improved due to the catalytic action of the zinc stearate.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, 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 invention.
It should be noted that the reagents or apparatuses used in the examples are not indicated by the manufacturer, but those not indicated by the specific techniques or conditions described in the literature in the art or by the specifications of the products are all conventional products commercially available.
The experimental drugs and reagents used in the examples of the present invention and the comparative examples are described below:
isocyanate: toluene diisocyanate, environmental protection technology of Jiangsu Rene;
organic compounds with hydroxyl group, namely poly adipic acid-diethylene glycol ester glycol, and Nanjing novalagen chemistry;
catalyst triethylene diamine, chemical industry of Jinan Ruita;
graphene, shandong Xiang Sho New Material Co., ltd;
dimethyl benzylamine as promoter, shandong Lifan chemical engineering;
zinc stearate, shandong Asahi chemical industry.
Example 1
The chain extender for degradable plastics comprises, by mass, 20 parts of isocyanate, 60 parts of an organic compound with hydroxyl groups, 0.05 part of a catalyst, 15 parts of a layered graphene carrier, 0.5 part of an accelerator and 1 part of zinc stearate.
The preparation method comprises the following steps:
adding a compound with hydroxyl into a reaction container, heating to 120 ℃, vacuumizing to remove water, then keeping the temperature at 120 ℃ for 2h, cooling to 80 ℃, adding isocyanate and a catalyst, introducing nitrogen, reacting at 85 ℃, monitoring the NCO value to 4.1%, and finishing the polycondensation reaction to obtain a polycondensation product;
step two, mixing the polycondensation product obtained in the step one with layered graphene, and adding an accelerator; heating the mixture to 150 ℃, applying a pressure of 4MPa, and stirring for 4 hours to ensure that the mixture and the mixture react fully; after stirring, standing and cooling to obtain a composite product;
and step three, uniformly mixing the composite product obtained in the step two and zinc stearate at a high speed of 200rpm in a high-speed stirrer at room temperature to prepare the chain extender.
Example 2
The chain extender for degradable plastics comprises, by mass, 35 parts of isocyanate, 75 parts of organic compound with hydroxyl, 0.1 part of catalyst, 10 parts of layered graphene carrier, 0.2 part of accelerator and 0.5 part of zinc stearate.
The preparation method comprises the following steps:
step one, adding a compound with hydroxyl into a reaction container, heating to 120 ℃, vacuumizing to remove moisture, then preserving heat at 120 ℃ for 2 hours, cooling to 80 ℃, adding isocyanate and a catalyst, introducing nitrogen, reacting at 85 ℃, monitoring an NCO value to 4.1%, and finishing polycondensation to obtain a polycondensation product;
step two, mixing the polycondensation product obtained in the step one with layered graphene, and adding an accelerator; heating the mixture to 200 ℃, applying 5MPa pressure, and stirring for 6 hours to ensure that the mixture and the mixture react fully; after stirring, standing and cooling to obtain a composite product;
and step three, uniformly mixing the composite product obtained in the step two and zinc stearate at a high speed of 200rpm in a high-speed stirrer at room temperature to prepare the chain extender.
Example 3
The chain extender for degradable plastics comprises, by mass, 30 parts of isocyanate, 70 parts of organic compound with hydroxyl, 0.05 part of catalyst, 10 parts of layered graphene carrier, 0.2 part of accelerator and 1 part of zinc stearate.
The preparation method comprises the following steps:
adding a compound with hydroxyl into a reaction container, heating to 120 ℃, vacuumizing to remove water, then keeping the temperature at 120 ℃ for 2h, cooling to 80 ℃, adding isocyanate and a catalyst, introducing nitrogen, reacting at 85 ℃, monitoring the NCO value to 4.1%, and finishing the polycondensation reaction to obtain a polycondensation product;
step two, mixing the polycondensation product obtained in the step one with layered graphene, and adding an accelerator; heating the mixture to 150 ℃, applying a pressure of 4MPa, and stirring for 4 hours to ensure that the mixture and the mixture react fully; after stirring, standing and cooling to obtain a composite product;
and step three, uniformly mixing the composite product obtained in the step two and zinc stearate at a high speed of 200rpm in a high-speed stirrer at room temperature to prepare the chain extender.
Example 4
The chain extender for degradable plastics comprises, by mass, 20 parts of isocyanate, 60 parts of an organic compound with hydroxyl groups, 0.1 part of a catalyst, 10 parts of a layered graphene carrier, 0.5 part of an accelerator and 1 part of zinc stearate.
The preparation method comprises the following steps:
adding a compound with hydroxyl into a reaction container, heating to 120 ℃, vacuumizing to remove water, then keeping the temperature at 120 ℃ for 2h, cooling to 80 ℃, adding isocyanate and a catalyst, introducing nitrogen, reacting at 85 ℃, monitoring the NCO value to 4.1%, and finishing the polycondensation reaction to obtain a polycondensation product;
step two, mixing the polycondensation product obtained in the step one with layered graphene, and adding an accelerator; heating the mixture to 150 ℃, applying a pressure of 4MPa, and stirring for 4 hours to ensure that the mixture and the mixture react fully; after stirring, standing and cooling to obtain a composite product;
and step three, uniformly mixing the composite product obtained in the step two and zinc stearate at a high speed of 200rpm in a high-speed stirrer at room temperature to prepare the chain extender.
Dispersibility verification
Comparative example 1
The chain extender for degradable plastics comprises, by mass, 20 parts of isocyanate, 60 parts of organic compound with hydroxyl groups and 0.05 part of catalyst.
The preparation method comprises the following steps:
adding a compound with hydroxyl into a reaction container, heating to 120 ℃, vacuumizing to remove water, then keeping the temperature at 120 ℃ for 2h, cooling to 80 ℃, adding isocyanate and a catalyst, introducing nitrogen, reacting at 85 ℃, monitoring the NCO value to 4.1%, and finishing the polycondensation reaction to obtain the chain extender.
Comparative example 2
The chain extender for degradable plastics comprises, by mass, 20 parts of isocyanate, 15 parts of a layered graphene carrier, 0.5 part of an accelerator and 1 part of zinc stearate.
The preparation method comprises the following steps:
mixing isocyanate and layered graphene, and adding an accelerator; heating the mixture to 150 ℃, applying a pressure of 4MPa, and stirring for 4 hours to ensure that the mixture and the mixture react fully; after stirring, standing and cooling to obtain a composite product;
and step two, uniformly mixing the composite product obtained in the step one and zinc stearate at a high speed of 200rpm in a high-speed stirrer at room temperature to prepare the chain extender.
Experimental groups were designed using the chain extenders obtained in each of examples 1 to 4 and comparative examples 1 to 2, respectively, and toluene diisocyanate was used as a blank group. And (2) carrying out chain extension reaction on the chain extenders adopted in each group and PBAT, adding PBAT with the melt index of 45g/10min into a co-rotating twin-screw extruder through a weightless feeding scale, heating the chain extenders to 80 ℃, metering and feeding the chain extenders into the extruder through a melt pump, setting the rotating speed of the screws to be 100rpm, completing the chain extension reaction in the co-rotating twin-screw extruder, and cooling, pelletizing and drying to obtain granules. The pellets were blown on a film blowing machine to a film thickness of 40 μm and a width of 500mm, the film was cut into a shape of 200X 200mm, and the number of crystal points (diameter >0.2 mm) was counted by placing the film on a glass plate. The number of crystal points can reflect the good dispersibility of the isocyanate chain extender in the degradable polyester, if the isocyanate chain extender is locally excessive, the product has crystal points, and the larger the number is, the poorer the dispersibility is. The test results are shown in table 1:
| grain point (diameter)>0.2 mm) number | |
| Example 1 | 1 |
| Example 2 | 0 |
| Example 3 | 0 |
| Example 4 | 0 |
| Comparative example 1 | 13 |
| Comparative example 2 | 6 |
| Blank group | 21 |
It can be found from the test data in Table 1 that the number of crystal points of examples 1-4 is zero or one. The chain extender provided by the invention shows good dispersion performance in the polyester chain extension reaction, so that no crystal points or a small number of crystal points appear in the product. This can be seen from the comparison of the blanks, the number of crystal points of the blanks reached 21, indicating that the isocyanate chain extender without any modification had poor dispersibility in the chain extension reaction of the polyester, and the appearance of local excess isocyanate resulted in the appearance of crystal points. In contrast to comparative example 1, which does not use the layered graphene as a carrier chain extender, in the polyester chain extension reaction, although the organic compound with hydroxyl groups helps to improve the dispersibility, so that the number of crystal points is reduced to 13, the dispersibility is still not good compared with examples 1 to 4. The chain extender of the comparative example 2 takes graphene as a carrier, so that the dispersity of the chain extender in the polyester chain extension reaction is effectively improved, the number of crystal points is reduced to 6, but the dispersity improvement effect is still not as good as that of the chain extender of the examples 1 to 4 due to the lack of modification of the hydroxyl-containing organic compound in the components. Through comparison of comparative examples 1-2 and blank groups, the invention proves that the dispersibility of the chain extender in the chain extension reaction can be effectively improved by using the graphene as the carrier, and the effect can be further improved by the organic compound with hydroxyl.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The chain extender for degradable plastics is characterized by comprising, by mass, 20-35 parts of isocyanate, 60-75 parts of organic compound with hydroxyl, 0.05-0.1 part of catalyst, 10-15 parts of layered graphene carrier, 0.2-0.5 part of accelerator and 0.5-1 part of zinc stearate.
2. The chain extender of claim 1, wherein the isocyanate is one or more of toluene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate, and cyclohexanedimethyl diisocyanate.
3. The chain extender for degradable plastics as claimed in claim 1, wherein the organic compound with hydroxyl group is one or more of poly (ethylene glycol adipate) glycol, poly (diethylene glycol adipate) glycol, poly (neopentyl glycol adipate) 1,4 butanediol glycol, poly (ethylene glycol adipate) glycol-diethylene glycol, or poly (adipic acid) 1,4-butanediol-diethylene glycol.
4. The chain extender for degradable plastics as claimed in claim 1, wherein the number average molecular weight of the organic compound with hydroxyl group is 400 to 8000Dalton.
5. The chain extender for degradable plastics as claimed in claim 1, wherein the catalyst is amine catalyst.
6. The chain extender for degradable plastics as claimed in claim 1, wherein the weight ratio of the isocyanate to the layered graphene carrier is 3:1.
7. The chain extender for degradable plastics as claimed in claim 1, wherein the accelerator is dimethylbenzylamine or monomethylimidazole.
8. A method for preparing the chain extender for degradable plastics as claimed in any one of claims 1 to 7, characterized by comprising the steps of:
step one, mixing isocyanate, an organic compound with hydroxyl and a catalyst, and carrying out polycondensation reaction to obtain a polycondensate for later use;
step two, mixing the polycondensate obtained in the step one with a layered graphene carrier, adding an accelerant, stirring at high temperature and high pressure to ensure that the polycondensate and the layered graphene carrier are fully reacted, standing and cooling to obtain a polymer for later use;
and step three, uniformly mixing the polymer obtained in the step two and zinc stearate at a high speed at room temperature to obtain the chain extender.
9. The method for preparing a chain extender for degradable plastics according to claim 8, wherein the temperature of the polycondensation reaction in the first step is 60 to 120 ℃.
10. The preparation method of the chain extender for degradable plastics according to claim 8, wherein the conditions of high temperature and high pressure in the second step are that the temperature is 150-200 ℃ and the pressure is 4-5 MPa.
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| CN106243309A (en) * | 2016-07-28 | 2016-12-21 | 东莞市雄林新材料科技股份有限公司 | A kind of bio-based TPU film and preparation method thereof |
| WO2018040506A1 (en) * | 2016-08-30 | 2018-03-08 | 久盛地板有限公司 | Polyurethane antimicrobial adhesive having graphene and preparation method therefor |
| CN112876646A (en) * | 2021-01-15 | 2021-06-01 | 华峰集团有限公司 | Modified chain extender and preparation method and application thereof |
| CN113717506A (en) * | 2021-09-30 | 2021-11-30 | 兰州大学 | Graphene-degradable resin master batch and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243309A (en) * | 2016-07-28 | 2016-12-21 | 东莞市雄林新材料科技股份有限公司 | A kind of bio-based TPU film and preparation method thereof |
| WO2018040506A1 (en) * | 2016-08-30 | 2018-03-08 | 久盛地板有限公司 | Polyurethane antimicrobial adhesive having graphene and preparation method therefor |
| CN112876646A (en) * | 2021-01-15 | 2021-06-01 | 华峰集团有限公司 | Modified chain extender and preparation method and application thereof |
| CN113717506A (en) * | 2021-09-30 | 2021-11-30 | 兰州大学 | Graphene-degradable resin master batch and preparation method and application thereof |
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