CN115433390B - Chain extender for degradable plastic and preparation method thereof - Google Patents
Chain extender for degradable plastic and preparation method thereof Download PDFInfo
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- CN115433390B CN115433390B CN202211234699.9A CN202211234699A CN115433390B CN 115433390 B CN115433390 B CN 115433390B CN 202211234699 A CN202211234699 A CN 202211234699A CN 115433390 B CN115433390 B CN 115433390B
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- 239000004970 Chain extender Substances 0.000 title claims abstract description 66
- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 31
- 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 28
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 19
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 16
- 238000006068 polycondensation reaction Methods 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 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 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
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-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
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- MTVMXNTVZNCVTH-UHFFFAOYSA-N ethane-1,2-diol;2-(2-hydroxyethoxy)ethanol Chemical compound OCCO.OCCOCCO MTVMXNTVZNCVTH-UHFFFAOYSA-N 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
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- FOUKZVYGNGOPLY-UHFFFAOYSA-N butane-1,4-diol;2,2-dimethylpropane-1,3-diol Chemical compound OCCCCO.OCC(C)(C)CO FOUKZVYGNGOPLY-UHFFFAOYSA-N 0.000 claims 1
- TWBIEWIPDPBRSU-UHFFFAOYSA-N butane-1,4-diol;2-(2-hydroxyethoxy)ethanol Chemical compound OCCCCO.OCCOCCO TWBIEWIPDPBRSU-UHFFFAOYSA-N 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 16
- 239000013078 crystal Substances 0.000 abstract description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 description 20
- 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
- -1 poly (1, 4-butanediol-diethylene glycol adipate Chemical compound 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920000704 biodegradable plastic Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 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
- 229920001002 functional polymer Polymers 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001896 polybutyrate Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group 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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 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
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction 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
- 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
- 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 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
- 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
- 238000003860 storage Methods 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 plastic 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. According to the chain extender for the degradable plastic, the lamellar graphene is used as a carrier, and the lamellar graphene is of a planar structure, so that the surface of the lamellar graphene contains a large number of active groups, the graphene has good dispersibility, the isocyanate chain extender is 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 can meet the use requirement of various properties of the product, has unchanged properties in the storage period and can degrade substances harmless to the environment under the natural environment condition after being used. There are various kinds of degradable plastics including photodegradable plastics, biodegradable plastics, photo/oxidative/bio-comprehensive degradable plastics, carbon dioxide-based biodegradable plastics, thermoplastic starch resin degradable plastics, etc. Biodegradable materials are currently one of the most effective ways to address white pollution. For biodegradable plastics, the structure of the biodegradable plastics often contains hydroxyl, carboxyl and other reactive groups, and molecular chain growth and crosslinking can be realized through a chain extender, so that the processing and application performances of products are improved, and the diversification of processing modes and application fields is realized.
Chain extenders, also known as chain extenders, are substances which react with functional groups on the linear polymer chains to extend the molecular chains and increase the molecular weight. Is commonly used for improving the mechanical property and the technological property of polyurethane, polyester and other products. The chain extender used so far mainly includes epoxy functional polymer chain extender, maleic anhydride functional polymer chain extender, isocyanate chain extender, oxazoline chain extender and the like.
At present, the isocyanate chain extender is often found to have good dispersibility in polyester, is easy to form gel or crystal points and affects the effect of the degradable polyester plastic finished product in use.
Disclosure of Invention
In order to solve the problems that the isocyanate chain extender mentioned in the background art is good in dispersibility in polyester, gel or crystal points are easy to form, and the effect of a degradable polyester plastic finished product is affected, the chain extender for the degradable plastic provided by the invention takes layered graphene as a carrier, and the surface of the layered graphene is of a planar structure, so that the graphene has good dispersibility, the isocyanate chain extender is 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 the degradable plastic 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 embodiments, 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 embodiments, it is preferable that the hydroxyl-bearing organic compound is one or more of a poly (ethylene glycol) adipate glycol, a poly (diethylene glycol) adipate glycol, a poly (neopentyl glycol) 1, 4-butanediol adipate glycol, a poly (ethylene glycol-diethylene glycol) adipate glycol or a poly (1, 4-butanediol-diethylene glycol adipate glycol).
In carrying out the above examples, it is preferable that the hydroxyl group-containing organic compound has a number average molecular weight of 400 to 8000 daltons.
In carrying out the above embodiment, preferably, the catalyst is an amine catalyst.
In implementing the above embodiment, preferably, the weight ratio of the isocyanate to the layered graphene carrier is 3:1.
In carrying out the above embodiments, preferably, the accelerator is dimethylbenzylamine or monomethyl imidazole.
On the other hand, the preparation method of the chain extender for the degradable plastic comprises the following steps:
step one, mixing isocyanate, an organic compound with hydroxyl and a catalyst, and performing polycondensation reaction to obtain a polycondensate for standby;
step two, mixing the polycondensate obtained in the step one with a layered graphene carrier, adding an accelerator, stirring at high temperature and high pressure to ensure that the polycondensate and the layered graphene carrier fully react, and standing and cooling to obtain a polymer for later use;
and thirdly, uniformly mixing the polymer obtained in the second step with zinc stearate at a high speed at room temperature to obtain the chain extender.
In carrying out the above examples, it is preferable that the temperature of the polycondensation reaction in the step one is 60 to 120 ℃.
In the implementation of the above embodiment, the conditions of high temperature and high pressure in the second step are preferably that the temperature is 150-200 ℃ and the pressure is 4-5 MPa.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the chain extender for the degradable plastic, the lamellar graphene is added, so that a polycondensation product of isocyanate and an organic compound with hydroxyl is taken as a carrier to obtain a composite product. The surface of the graphene 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 reactivity, so that the good dispersion of the isocyanate chain extender in the degradable polyester is improved, the local excess of isocyanate is avoided, and the problem of gel or crystal point of the product is solved. In addition, the addition of the layered graphene can improve the rigidity of the polyester resin.
2. The chain extender for the degradable plastic further improves the dispersibility of the chain extender in the biological polyester by modifying isocyanate with the hydroxyl organic compound. Meanwhile, the modified chain extender is easier to control the reactivity of the isocyanate chain extender and the hydroxyl in the polyester, and the production process is more stable and easy to control.
3. The active groups contained on the surface of the graphene added by the chain extender for the degradable plastic can react with groups on polyester, so that the branching degree is further improved. In addition, zinc stearate is added, so that the ring-opening reaction of epoxy groups on graphene can be catalyzed, the chain extension temperature is reduced, and the utilization rate of the epoxy groups is obviously improved due to the catalysis of the zinc stearate.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, in the examples, specific techniques or conditions are not noted, and the reagents or apparatuses used, which are carried out according to techniques or conditions described in the literature in the field or according to the specifications of the products, are conventional products commercially available, and are not noted to manufacturers.
The experimental drugs and reagents adopted in the embodiment and the comparative example of the invention are described as follows:
isocyanate: toluene diisocyanate, jiangsu Lorente environmental protection technology;
organic compound with hydroxyl group, namely poly adipic acid-diethylene glycol ester diol and Nanjing's new chemical;
catalyst is triethylene diamine, jinan Runtai chemical industry;
graphene, shandong Xiangshaonovel materials Co., ltd;
the accelerator is dimethylbenzylamine, and is used in Shandong Lifan chemical industry;
zinc stearate, shandong Xu Chen Cao.
Example 1
The chain extender for the degradable plastic comprises, by mass, 20 parts of isocyanate, 60 parts of organic compound with hydroxyl, 0.05 part of catalyst, 15 parts of layered graphene carrier, 0.5 part of accelerator and 1 part of zinc stearate.
The preparation method comprises the following steps:
step one, adding a hydroxyl compound into a reaction container, heating to 120 ℃, vacuumizing, removing water, preserving heat at 120 ℃ for 2 hours, cooling to 80 ℃, adding isocyanate and a catalyst, introducing nitrogen for reaction at 85 ℃, monitoring the NCO value to 4.1%, and ending the reaction to obtain a polycondensation product;
step two, mixing the polycondensation product of the step one with the layered graphene, and adding an accelerator; heating the mixture to 150 ℃, applying pressure of 4MPa, and stirring for 4 hours to ensure that the two 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 with zinc stearate in a high-speed stirrer at a high speed of 200rpm at room temperature to obtain the chain extender.
Example 2
The chain extender for the degradable plastic 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 hydroxyl compound into a reaction container, heating to 120 ℃, vacuumizing, removing water, preserving heat at 120 ℃ for 2 hours, cooling to 80 ℃, adding isocyanate and a catalyst, introducing nitrogen for reaction at 85 ℃, monitoring the NCO value to 4.1%, and ending the reaction to obtain a polycondensation product;
step two, mixing the polycondensation product of the step one with the layered graphene, and adding an accelerator; heating the mixture to 200 ℃, applying 5MPa pressure, and stirring for 6 hours to ensure that the two 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 with zinc stearate in a high-speed stirrer at a high speed of 200rpm at room temperature to obtain the chain extender.
Example 3
The chain extender for the degradable plastic 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:
step one, adding a hydroxyl compound into a reaction container, heating to 120 ℃, vacuumizing, removing water, preserving heat at 120 ℃ for 2 hours, cooling to 80 ℃, adding isocyanate and a catalyst, introducing nitrogen for reaction at 85 ℃, monitoring the NCO value to 4.1%, and ending the reaction to obtain a polycondensation product;
step two, mixing the polycondensation product of the step one with the layered graphene, and adding an accelerator; heating the mixture to 150 ℃, applying pressure of 4MPa, and stirring for 4 hours to ensure that the two 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 with zinc stearate in a high-speed stirrer at a high speed of 200rpm at room temperature to obtain the chain extender.
Example 4
The chain extender for the degradable plastic comprises, by mass, 20 parts of isocyanate, 60 parts of organic compound with hydroxyl, 0.1 part of catalyst, 10 parts of layered graphene carrier, 0.5 part of accelerator and 1 part of zinc stearate.
The preparation method comprises the following steps:
step one, adding a hydroxyl compound into a reaction container, heating to 120 ℃, vacuumizing, removing water, preserving heat at 120 ℃ for 2 hours, cooling to 80 ℃, adding isocyanate and a catalyst, introducing nitrogen for reaction at 85 ℃, monitoring the NCO value to 4.1%, and ending the reaction to obtain a polycondensation product;
step two, mixing the polycondensation product of the step one with the layered graphene, and adding an accelerator; heating the mixture to 150 ℃, applying pressure of 4MPa, and stirring for 4 hours to ensure that the two 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 with zinc stearate in a high-speed stirrer at a high speed of 200rpm at room temperature to obtain the chain extender.
Dispersibility verification
Comparative example 1
The chain extender for the degradable plastic comprises, by mass, 20 parts of isocyanate, 60 parts of organic compound with hydroxyl and 0.05 part of catalyst.
The preparation method comprises the following steps:
adding a hydroxyl compound into a reaction container, heating to 120 ℃, vacuumizing, removing water, preserving heat at 120 ℃ for 2 hours, cooling to 80 ℃, adding isocyanate and a catalyst, introducing nitrogen, reacting at 85 ℃, monitoring the NCO value to 4.1%, and ending the polycondensation reaction to obtain the chain extender.
Comparative example 2
The chain extender for the degradable plastic 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:
step one, mixing isocyanate and lamellar graphene, and adding an accelerator; heating the mixture to 150 ℃, applying pressure of 4MPa, and stirring for 4 hours to ensure that the two 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 in a high-speed stirrer at a high speed of 200rpm at room temperature to obtain the chain extender.
The chain extenders obtained in each of examples 1-4 and comparative examples 1-2 were each designed into experimental groups and toluene diisocyanate was used as a blank group. And (3) carrying out chain extension reaction on the chain extender adopted by each group and PBAT, adding the PBAT with the melt index of 45g/10min into a homodromous double-screw extruder through a weightless feeding scale, heating the chain extender to 80 ℃, metering and feeding the chain extender into the extruder through a melt pump, setting the screw rotating speed to 100rpm, completing the chain extension reaction in the homodromous double-screw extruder, cooling, granulating, and drying to obtain the granules. The pellets were blown on a film blowing machine with 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 spots (diameter >0.2 mm) was counted on a glass plate. The number of crystal points can reflect the good dispersibility of the isocyanate chain extender in the degradable polyester, and if the isocyanate chain extender is locally excessive, the crystal points of the product can appear, and the larger the number is, the worse the dispersibility is. The test results are shown in Table 1:
| crystal 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 |
As can be seen from the test data in Table 1, examples 1-4 have zero or one number of spots. Proved by the invention, the chain extender provided by the invention has good dispersion performance in the polyester chain extension reaction, so that the number of the amorphous spots of the product is small. This can be seen from a comparison of the blank groups, the number of crystal dots of which reaches 21, indicating that the dispersibility of the isocyanate chain extender in the chain extension reaction of the polyester is poor without any modification, and that local isocyanate excess occurs to cause crystal dots to appear. In contrast to comparative example 1, which did not use a chain extender based on layered graphene, although the hydroxyl-containing organic compound was helpful in improving the dispersibility thereof in the polyester chain extension reaction, so that the number of crystal grains was reduced to 13, the dispersibility thereof was still inferior to examples 1 to 4. The chain extender of comparative example 2 uses graphene as a carrier, effectively improves the dispersibility of the chain extender in the polyester chain extension reaction, and reduces the number of crystal points to 6, but the dispersibility improvement effect is still not as good as that of examples 1-4 due to the lack of modification of the hydroxyl-bearing organic compound in the components. Through comparison of comparative examples 1-2 and blank groups, it is proved that the dispersibility of the chain extender in the chain extension reaction can be effectively improved by taking graphene as a 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 for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. The chain extender for the degradable plastic 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; the preparation method of the chain extender comprises the following steps:
step one, mixing isocyanate, an organic compound with hydroxyl and a catalyst, and performing polycondensation reaction to obtain a polycondensate for standby;
step two, mixing the polycondensate obtained in the step one with a layered graphene carrier, adding an accelerator, stirring at high temperature and high pressure to ensure that the polycondensate and the layered graphene carrier fully react, and standing and cooling to obtain a polymer for later use;
and thirdly, uniformly mixing the polymer obtained in the second step with zinc stearate at a high speed at room temperature to obtain the chain extender.
2. The chain extender for degradable plastics according to 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 of claim 1, wherein the hydroxyl-bearing organic compound is one or more of poly (ethylene glycol) adipate glycol, poly (diethylene glycol) adipate glycol, poly (neopentyl glycol-1, 4-butanediol) adipate glycol, poly (ethylene glycol-diethylene glycol) adipate glycol or poly (1, 4-butanediol-diethylene glycol) adipate glycol.
4. The chain extender for degradable plastics according to claim 1, wherein the hydroxyl-bearing organic compound has a number average molecular weight of 400 to 8000 daltons.
5. The chain extender for degradable plastics of claim 1, wherein the catalyst is an amine type catalyst.
6. The chain extender for degradable plastics of claim 1, wherein the weight ratio of isocyanate to lamellar graphene carrier is 3:1.
7. The chain extender for degradable plastics of claim 1, wherein the accelerator is dimethylbenzylamine.
8. The chain extender for degradable plastics of claim 1, wherein the temperature of the polycondensation reaction in step one is 60 to 120 ℃.
9. The chain extender for degradable plastics of claim 1, 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 |
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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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