CN117624692A - Low-carbon biodegradable composite membrane and preparation method and application thereof - Google Patents
Low-carbon biodegradable composite membrane and preparation method and application thereof Download PDFInfo
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- CN117624692A CN117624692A CN202410103017.3A CN202410103017A CN117624692A CN 117624692 A CN117624692 A CN 117624692A CN 202410103017 A CN202410103017 A CN 202410103017A CN 117624692 A CN117624692 A CN 117624692A
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000012528 membrane Substances 0.000 title claims description 16
- 229920006264 polyurethane film Polymers 0.000 claims abstract description 86
- 239000004814 polyurethane Substances 0.000 claims abstract description 81
- 229920002635 polyurethane Polymers 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000004970 Chain extender Substances 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 239000011241 protective layer Substances 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 15
- 238000007731 hot pressing Methods 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004945 emulsification Methods 0.000 claims description 11
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 10
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 10
- 150000003384 small molecules Chemical group 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- XOIJCNLAQGFSAY-ARJAWSKDSA-N (Z)-4-(dihydroxyamino)-2-ethyl-4-oxobut-2-enoic acid Chemical compound ON(C(\C=C(/C(=O)O)\CC)=O)O XOIJCNLAQGFSAY-ARJAWSKDSA-N 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- RXZHXOJAHDKBKK-UHFFFAOYSA-N 2-(2-aminoethylamino)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)NCCN RXZHXOJAHDKBKK-UHFFFAOYSA-N 0.000 claims description 2
- BVIXTPMSXQAQBG-UHFFFAOYSA-N 2-(2-hydroxyethylamino)ethanesulfonic acid Chemical compound OCCNCCS(O)(=O)=O BVIXTPMSXQAQBG-UHFFFAOYSA-N 0.000 claims description 2
- 238000003854 Surface Print Methods 0.000 claims description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 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 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000009264 composting Methods 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 32
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 25
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 25
- 238000001816 cooling Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000001804 emulsifying effect Effects 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000003916 ethylene diamine group Chemical group 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical group CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The application belongs to the technical field of printing and packaging, and particularly relates to a low-carbon biodegradable composite film, and a preparation method and application thereof; the low-carbon biodegradable composite film prepared by the preparation method is obtained by reacting carbon dioxide polymer polyol serving as a reaction substrate with isocyanate and then using a chain extender to react, wherein a molecular chain contains a large number of carbonate bonds and ether bonds, the content of intermolecular and intramolecular hydrogen bonds is high, the cohesive energy is high, the dryness is high, and the composite film can be degraded by composting; the polyurethane with high viscous flow temperature is used as the outer surface, the polyurethane with low viscous flow temperature is used as the inner surface, and the polyurethane is used for hot-pressing the low-carbon biodegradable composite film onto the surface of the printed pattern of the paper surface, so as to provide durable protection, and solve the technical problems that the polyurethane film in the prior art is difficult to biodegrade and has poor dryness and is not suitable for being used as a protective layer of the printed pattern of the paper surface.
Description
Technical Field
The application belongs to the technical field of printing and packaging, and particularly relates to a low-carbon biodegradable composite film, and a preparation method and application thereof.
Background
The surfaces of some books, brochures and other papers are provided with printed patterns, and in order to protect the printed patterns, a BOPP film with the inner surface coated with hot melt adhesive is adhered to the surface of the papers by a hot pressing process, and the papers with the surfaces coated with the BOPP film have improved wear resistance, folding resistance, pulling resistance, moisture resistance and decoration performance; however, the BOPP film is difficult to fall off from the surface of the waste paper, the treatment cost is high, and meanwhile, the BOPP film made of polypropylene is a non-degradable film, so that the recycling is difficult, and the environmental pollution and the resource waste are easily caused.
At present, some aqueous polyurethane has the potential of replacing BOPP films to protect printed patterns on the surface of paper, for example, polyether aqueous polyurethane emulsion can be coated on the surface of paper to replace BOPP films to protect the paper after being dried to form films, however, the polyether aqueous polyurethane has higher soft segment content, lower hard segment content and poor dryness, and meanwhile, the polyether aqueous polyurethane is a non-biodegradable material, so that the recycling problem still exists after the use. The polyester type aqueous polyurethane emulsion can be coated on the surface of paper, and the paper is protected by replacing a BOPP film after being dried to form a film, however, the polyester type aqueous polyurethane is easy to hydrolyze in a humid environment, the surface starts to be sticky after a period of use, the dryness is poor, and the service life is short; thus, there is currently a lack of biodegradable and durable polyurethane films to provide efficient protection for papers such as book covers, brochures, etc. having surface printed graphics.
Disclosure of Invention
In view of the above, the application provides a low-carbon biodegradable composite film, a preparation method and application thereof, which are used for solving the technical problems that a polyurethane film is difficult to biodegrade and poor in dryness and is not suitable for being used as a protective layer for printing patterns on the surface of paper in the prior art.
The first aspect of the present application provides a method for preparing a low-carbon biodegradable composite membrane, which can prepare the low-carbon biodegradable composite membrane of the first aspect, and comprises the following steps:
step S1, coating aqueous polyurethane B emulsion on the surface of a removable template, and drying to form a film to obtain an aqueous polyurethane film B;
s2, coating aqueous polyurethane A emulsion on the surface of the aqueous polyurethane film B, drying the aqueous polyurethane A emulsion to form a film, and removing a template to obtain a low-carbon biodegradable composite film;
the preparation method of the aqueous polyurethane A emulsion comprises the following steps: the preparation method comprises the steps of carrying out prepolymerization reaction on carbon dioxide polymer polyol, a hydrophilic chain extender and isocyanate, and then sequentially carrying out salification reaction, emulsification reaction, adding a small molecule chain extender and chain extension reaction to obtain the polyurethane polymer;
the preparation method of the aqueous polyurethane B emulsion comprises the following steps: the preparation method comprises the steps of carrying out prepolymerization reaction on carbon dioxide polymer polyol, a hydrophilic chain extender and isocyanate, sequentially carrying out salification reaction, emulsification reaction and chain extension reaction by adding a chain extender.
Preferably, the small molecule chain extender is at least one selected from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
Preferably, the chain-extending cross-linking agent is at least one selected from ethylenediamine, propylenediamine and butylenediamine.
Preferably, the carbon dioxide polymer polyol is synthesized by taking carbon dioxide as a starting material, adding an initiator, and carrying out catalytic reaction and copolymerization with propylene oxide.
Preferably, the hydrophilic chain extender is selected from at least one of N, N-dihydroxyethyl monomaleamic acid, dimethylolpropionic acid, dimethylolbutyric acid, N- (2-hydroxyethyl) -2-aminoethanesulfonic acid and N- (2-aminoethyl) -2-aminopropanesulfonic acid;
the isocyanate is at least one selected from toluene diisocyanate TDI, hydrogenated diphenylmethane diisocyanate HMDI, isophorone diisocyanate IPDI and hexamethylene diisocyanate HDI;
the catalyst used in the prepolymerization reaction is stannous octoate;
the salifying agent used in the salifying reaction is at least one of triethylamine, tripropylamine, tributylamine, sodium hydroxide and potassium hydroxide;
the solvent used in the emulsification reaction is water.
Preferably, in the step S1, the drying temperature is 60-80 ℃ and the drying time is 0.5-4 hours;
in the step S2, the drying temperature is 40-70 ℃ and the drying time is 0.5-4 h.
Preferably, the temperature of the prepolymerization reaction is 40-100 ℃ and the time is 0.5-4 hours;
the temperature of the salification reaction is 20-40 ℃ and the time is 0.1-1 h;
the temperature of the emulsification reaction is-20-0 ℃ and the time is 0.1-1 h;
the temperature of the chain extension reaction is-20-0 ℃ and the time is 0.1-1 h.
Preferably, the raw materials of the aqueous polyurethane A emulsion comprise, in parts by mass: 100 parts of carbon dioxide polymer polyol, 3-10 parts of hydrophilic chain extender, 20-50 parts of polyisocyanate, 1-10 parts of micromolecular chain extender, 0.02-0.3 part of catalyst, 2-10 parts of salifying agent and 100-300 parts of deionized water.
Preferably, the raw materials of the aqueous polyurethane B emulsion comprise the following components in parts by mass: 100 parts of carbon dioxide polymer polyol, 3-10 parts of hydrophilic chain extender, 20-50 parts of polyisocyanate, 1-10 parts of micromolecular chain extender cross-linking agent, 0.02-0.3 part of catalyst, 2-10 parts of salifying agent and 100-300 parts of deionized water.
Preferably, in step S2, the removable template is BOPP film.
The second aspect of the application provides a low-carbon biodegradable composite film, which comprises an aqueous polyurethane film A on the inner surface and an aqueous polyurethane film B on the outer surface;
the aqueous polyurethane film A is obtained after the aqueous polyurethane A emulsion in the first aspect is dried to form a film;
the aqueous polyurethane film B is obtained by drying the aqueous polyurethane B emulsion to form a film.
Preferably, the thickness of the aqueous polyurethane film A is 5-50 mu m;
the thickness of the aqueous polyurethane film B is 5-50 mu m.
Preferably, the thickness of the aqueous polyurethane film A is 10-30 mu m;
the thickness of the aqueous polyurethane film B is 10-20 mu m.
The third invention provides application of the low-carbon biodegradable composite film in the field of paper surface printing pattern protection.
Preferably, the application in the field of protecting printed patterns on the surface of paper specifically comprises: and covering the water-based polyurethane film A on the surface of the printing pattern of the paper, and hot-pressing one side of the water-based polyurethane film B to form a low-carbon biodegradable composite film protective layer on the surface of the printing pattern.
Preferably, the hot pressing temperature is higher than the viscous flow temperature of the aqueous polyurethane film A and lower than the viscous flow temperature of the aqueous polyurethane film B.
In summary, the application provides a low-carbon biodegradable composite film, a preparation method and an application thereof, wherein the low-carbon biodegradable composite film prepared by the preparation method comprises an inner surface of a water-based polyurethane film A and an outer surface of a water-based polyurethane film B, and the water-based polyurethane film A and the water-based polyurethane film B are obtained by reacting carbon dioxide polymer polyol serving as a reaction substrate with isocyanate and then reacting with a chain extender, so that the molecular structures of the water-based polyurethane component films A and B all contain a large amount of carbonate bonds and ether bonds, the intermolecular and intramolecular hydrogen bond contents are high, the cohesive energy is high, the dryness is high, the films are not easy to adhere to each other in the storage process, and the films can be degraded under the composting condition to be biodegradable polyurethane films; and the aqueous polyurethane film A and the aqueous polyurethane film B adopt different chain extenders in the chain extension reaction to obtain the aqueous polyurethane film with different crosslinking degrees and different adhesive flow temperatures, the adhesive flow temperature of the aqueous polyurethane film A on the inner surface is low, which is favorable for hot press molding, and the adhesive flow temperature of the aqueous polyurethane film B on the outer surface is high, which is favorable for providing durable protection, thereby solving the technical problems that the polyurethane film is difficult to biodegrade and has poor dryness and is not suitable for being used as a protective layer for printing patterns on the surface of paper in the prior art.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an infrared spectrogram of a water-based polyurethane film a and a water-based polyurethane film B of the low-carbon biodegradable composite film prepared in example 1 of the present application.
FIG. 2 is a schematic diagram of a preparation flow and a structural formula of a product of a carbon dioxide polymer polyol as a preparation raw material used in the application, wherein the molecular weight of the carbon dioxide polymer polyol is 2000-3000;
FIG. 3 is a schematic diagram of the preparation flow and the structural formula of the product of the aqueous polyurethane emulsion B in the low-carbon biodegradable composite membrane obtained in example 1 of the present application;
in FIG. 3, R 1 、R 2 、R 3 、R 4 The structure of (a) is as follows:
；
；
；
。
Detailed Description
The application provides a low-carbon biodegradable composite film, a preparation method and application thereof, which are used for solving the technical problems that a polyurethane film is difficult to biodegrade and poor in dryness and is not suitable for being used as a protective layer for printing patterns on the surface of paper in the prior art.
The following description of the embodiments of the present application will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
In view of the potential of replacing BOPP films at present, polyurethane films such as polyether aqueous polyurethane and polyester aqueous polyurethane which can be used for protecting printed patterns on the surface of paper have the defects of difficult biodegradation, poor dryness and inapplicability to being used as protective layers for printed patterns on the surface of paper, the embodiment of the application provides a novel aqueous polyurethane film, which is specifically a low-carbon biodegradable composite film, comprising an aqueous polyurethane film A on the inner surface and an aqueous polyurethane film B on the outer surface, wherein the aqueous polyurethane film A faces to one side of printed patterns on the surface of paper, and the aqueous polyurethane film B faces to one side of printed patterns on the surface of paper.
The aqueous polyurethane film A and the aqueous polyurethane film B on the outer surface of the low-carbon biodegradable composite film are both obtained by reacting carbon dioxide polymer polyol as a reaction substrate with isocyanate and then reacting with a chain extender, wherein a molecular chain contains a large amount of carbonate bonds and ether bonds, the intermolecular and intramolecular hydrogen bonds have high content, the cohesive energy is high, the films are not easy to adhere in the storage process, meanwhile, the biodegradability of the polyurethane film taking the carbon dioxide polymer polyol as the reaction substrate is excellent, and experiments show that the relative biodegradation rate of the polyurethane film taking the carbon dioxide polymer polyol as the reaction substrate reaches 90% under the composting condition, so that the polyurethane film belongs to compostable degradable materials; in addition, the adopted chain extender is ethylenediamine chain extender cross-linking agent in the chain extension reaction process of the aqueous polyurethane component film B, partial molecular chains of the aqueous polyurethane component film B are cross-linked into a net structure, and the cross-linking degree is improved, so that the adhesive flow temperature of the aqueous polyurethane component film B serving as the outer surface is higher than that of the aqueous polyurethane component film A serving as the inner surface, when patterns are printed on the surface of paper in a covering manner, the protective effect of the aqueous polyurethane component film B with high adhesive flow temperature is high, the aqueous polyurethane component film B cannot be melted at high temperature, deformation is generated, the durability is good, the butanediol chain extender is adopted in the chain extension reaction process of the aqueous polyurethane component film A, the ethylenediamine chain extender is not adopted, and the cross-linking degree of the aqueous polyurethane component film A is low, thereby the adhesive flow temperature of the aqueous polyurethane component film A serving as the inner surface is lower than that of the aqueous polyurethane component film B serving as the outer surface, the aqueous polyurethane component film A on the inner surface is easy to be melted and then adhered to the surface of the paper in the hot pressing process, the phenomenon such as melting and the like cannot occur, so that the defects that the existing polyurethane film is difficult to biodegrade and the dry and the aqueous polyurethane component film is not suitable for printing patterns on the surface are overcome.
Meanwhile, the application also provides a preparation method of the low-carbon biodegradable composite membrane, which comprises the following steps: firstly, coating aqueous polyurethane B emulsion on the surface of a removable template BOPP film, and drying to form a film to obtain an aqueous polyurethane film B; then coating aqueous polyurethane A emulsion on the surface of the aqueous polyurethane film B, drying the aqueous polyurethane A emulsion to form a film, and removing the BOPP film to obtain a low-carbon and biodegradable composite film, wherein the low-carbon and biodegradable composite film is stored; wherein, the aqueous polyurethane film A emulsion and the aqueous polyurethane film B emulsion are obtained by carrying out prepolymerization reaction on carbon dioxide polymer polyol, hydrophilic chain extender and isocyanate, then sequentially carrying out salification reaction, emulsification reaction and chain extension reaction by adding the chain extender; the aqueous polyurethane film A emulsion uses chain extenders such as ethylene glycol in the chain extension reaction, and the aqueous polyurethane film B emulsion uses chain extension crosslinking agents such as ethylene diamine in the chain extension reaction, so that the crosslinking degree of the aqueous polyurethane film B after the aqueous polyurethane film B emulsion is dried is high.
Preferably, the application also provides application of the low-carbon biodegradable composite membrane, wherein the application process directly adopts the newly prepared low-carbon biodegradable composite membrane; the application process comprises the following steps: firstly, coating aqueous polyurethane B emulsion on the surface of a removable template BOPP film, and drying to form a film to obtain an aqueous polyurethane film B; coating aqueous polyurethane A emulsion on the surface of an aqueous polyurethane film B, drying to form a film, removing the BOPP film, covering the low-carbon biodegradable composite film with the BOPP film on the surface of the printed pattern of the paper, performing hot pressing, controlling the hot pressing temperature to be higher than the viscous flow temperature of the aqueous polyurethane film A and lower than the viscous flow temperature of the aqueous polyurethane film B, and removing the BOPP film after the hot pressing is finished, so as to obtain the low-carbon biodegradable composite film applied as the protective layer of the printed pattern of the paper surface; the viscous flow temperature of the aqueous polyurethane film A is 80-100 ℃, and the viscous flow temperature of the aqueous polyurethane film B is more than 180 ℃, so that the hot pressing temperature in the application is controlled within a temperature range of more than 80 ℃ but not more than 180 ℃.
The low-carbon biodegradable composite film used as the protective layer of the printed patterns on the surface of the paper can overcome the defect that the recycling of the paper is difficult after the traditional BOPP film is used as the protective layer of the printed patterns on the surface of the paper, and also avoid the defect that the traditional BOPP film needs to use ozone-corona treatment to produce ozone pollution when producing the protective layer of the printed patterns on the surface of the paper and cause great damage to the staff body.
In order to further explain the low-carbon biodegradable composite membrane provided by the application, the preparation method and application of the low-carbon biodegradable composite membrane will be specifically described below with reference to examples.
Example 1
The embodiment 1 of the application provides an embodiment of a low-carbon biodegradable composite film, which comprises a preparation step of preparing an aqueous polyurethane A emulsion in the low-carbon biodegradable composite film, a preparation step of an aqueous polyurethane B emulsion and an application process of directly adopting the newly prepared low-carbon biodegradable composite film as a protective layer of a printing pattern on the surface of paper.
The preparation method of the aqueous polyurethane A emulsion comprises the following steps:
after dehydration of 100g of carbon dioxide polymer glycol with molecular weight of 3000, 6.5g of 2, 2-dimethylolpropionic acid, 30g of isophorone diisocyanate and 0.2g of stannous octoate catalyst are added for reaction for 4 hours at 85 ℃, the temperature is reduced to 50-65 ℃, 0.2g of small molecule chain extender 1, 4-butanediol is added for reaction at 65-75 ℃ until the-NCO content reaches the theoretical value, the temperature is reduced to 40 ℃, acetone is added for regulating the viscosity, then 4.9g of triethylamine is added for reaction for 15 minutes, 250g of deionized water is added for emulsification at 0 ℃ for 20 minutes, then 1g of 1, 4-butanediol is added for reaction for 1 hour, and acetone is removed under reduced pressure, so that aqueous polyurethane A emulsion is obtained.
The preparation method of the aqueous polyurethane B emulsion comprises the following steps:
after dehydration of 100g of carbon dioxide polymer glycol with molecular weight of 3000, adding 6.65g of 2, 2-dimethylolpropionic acid, 34g of isophorone diisocyanate and 0.2g of stannous octoate catalyst, reacting for 4 hours at 85 ℃, cooling to 50-65 ℃, adding 0.5g of small molecule chain extender 1, 4-butanediol, reacting at 65-75 ℃ until the-NCO content reaches a theoretical value, cooling to 40 ℃, adding acetone to adjust the viscosity, then adding 5.01g of triethylamine, reacting for 15 minutes, adding 250g of deionized water, emulsifying for 20 minutes at 0 ℃, then adding 2.11g of ethylenediamine, reacting for 1 hour, and decompressing to remove acetone to obtain the aqueous polyurethane B emulsion.
The application process of the biodegradable composite film as the protective layer of the printed pattern on the surface of the paper comprises the following steps:
firstly, coating a BOPP film with a water-based polyurethane emulsion B, drying at 80 ℃ for 2 hours to obtain a water-based polyurethane film B serving as an outer surface, then coating a water-based polyurethane emulsion A on the water-based polyurethane film B, and drying at 80 ℃ for 2 hours to obtain a water-based polyurethane film A serving as an inner surface; and then, attaching the water-based polyurethane film to the surface of the paper at the temperature of 95 ℃, hot-pressing the paper, and removing the BOPP film to form the low-carbon biodegradable composite film on the surface of the paper, thereby realizing the protection of the paper.
Example 2
The embodiment 2 of the application provides an embodiment of a low-carbon biodegradable composite film, which comprises a preparation step of preparing an aqueous polyurethane A emulsion in the low-carbon biodegradable composite film, a preparation step of an aqueous polyurethane B emulsion and an application process of directly adopting the newly prepared low-carbon biodegradable composite film as a protective layer of a printing pattern on the surface of paper.
The preparation method of the aqueous polyurethane A emulsion comprises the following steps:
after dehydration of 100g of carbon dioxide polymer glycol with molecular weight of 3000, adding 6.5g of 2, 2-dimethylolpropionic acid, 26g of isophorone diisocyanate and 0.2g of stannous octoate catalyst, reacting for 4 hours at 85 ℃, cooling to 50-65 ℃, adding 0.3 small molecule chain extender diethylene glycol, reacting at 65-75 ℃ until the-NCO content reaches a theoretical value, cooling to 40 ℃, adding acetone to adjust viscosity, then adding 4.9g of triethylamine, reacting for 15 minutes, adding 250g of deionized water, emulsifying for 20 minutes at 0 ℃, then adding 0.6g of 1, 4-butanediol, reacting for 1 hour, and removing acetone under reduced pressure to obtain the aqueous polyurethane A emulsion.
The preparation method of the aqueous polyurethane B emulsion comprises the following steps:
after dehydration of 100g of carbon dioxide polymer glycol with molecular weight of 3000, adding 5g of 2, 2-dimethylolpropionic acid, 25g of isophorone diisocyanate and 0.2g of stannous octoate catalyst, reacting for 4 hours at 85 ℃, cooling to 50-65 ℃, adding 0.6g of micromolecular chain extender diethylene glycol, reacting at 65-75 ℃ until the-NCO content reaches a theoretical value, cooling to 40 ℃, adding acetone to adjust viscosity, adding 3.77g of triethylamine, reacting for 15 minutes, adding 250g of deionized water, emulsifying for 20 minutes at 0 ℃, adding 1.26g of ethylenediamine, reacting for 1 hour, and decompressing to remove acetone to obtain aqueous polyurethane B emulsion.
The application process of the biodegradable composite film as the protective layer of the printed pattern on the surface of the paper comprises the following steps:
firstly, coating a BOPP film with a water-based polyurethane emulsion B, drying at 80 ℃ for 2 hours to obtain a water-based polyurethane film B serving as an outer surface, then coating a water-based polyurethane emulsion A on the water-based polyurethane film B, and drying at 80 ℃ for 2 hours to obtain a water-based polyurethane film A serving as an inner surface; and then, attaching the water-based polyurethane film to the surface of the paper at the temperature of 90 ℃, hot-pressing the water-based polyurethane film to the surface of the paper, and removing the BOPP film to form the low-carbon biodegradable composite film on the surface of the paper, thereby realizing the protection of the paper.
Example 3
The embodiment 3 of the application provides an embodiment of a low-carbon biodegradable composite film, which comprises a preparation step of preparing an aqueous polyurethane A emulsion in the low-carbon biodegradable composite film, a preparation step of an aqueous polyurethane B emulsion and an application process of directly adopting the newly prepared low-carbon biodegradable composite film as a protective layer of a printing pattern on the surface of paper.
The preparation method of the aqueous polyurethane A emulsion comprises the following steps:
after dehydration of 100g of carbon dioxide polymer glycol with molecular weight of 3000, 6.35g of 2, 2-dimethylolpropionic acid, 19.7g of isophorone diisocyanate, 7.5g of hexamethylene diisocyanate and 0.3g of stannous octoate catalyst are added for reaction for 4 hours at 85 ℃, the temperature is reduced to 50-65 ℃,0.3g of small molecule chain extender 1, 6-hexanediol is added for reaction until the-NCO content reaches a theoretical value at 65-75 ℃, the temperature is reduced to 40 ℃, acetone is added for regulating the viscosity, then 4.79g of triethylamine is added for reaction for 15 minutes, 250g of deionized water is added for emulsification for 20 minutes at 0 ℃, then 0.9g of 1, 4-butanediol is added for reaction for 1 hour, and acetone is removed under reduced pressure to obtain aqueous polyurethane A emulsion.
The preparation method of the aqueous polyurethane B emulsion comprises the following steps:
after dehydration of 100g of carbon dioxide polymer glycol with molecular weight of 2000, adding 5g of 2, 2-dimethylolpropionic acid, 28g of isophorone diisocyanate and 0.2g of stannous octoate catalyst, reacting for 4 hours at 85 ℃, cooling to 50-65 ℃, adding 1g of small molecule chain extender 1, 6-hexanediol, reacting at 65-75 ℃ until the-NCO content reaches a theoretical value, cooling to 40 ℃, adding acetone to adjust the viscosity, then adding 3.77g of triethylamine, reacting for 15 minutes, adding 250g of deionized water, emulsifying for 20 minutes at 0 ℃, then adding 1.16g of ethylenediamine, reacting for 1 hour, and decompressing to remove acetone to obtain the aqueous polyurethane B emulsion.
The application process of the biodegradable composite film as the protective layer of the printed pattern on the surface of the paper comprises the following steps:
firstly, coating a BOPP film with a water-based polyurethane emulsion B, drying at 80 ℃ for 2 hours to obtain a water-based polyurethane film B serving as an outer surface, then coating a water-based polyurethane emulsion A on the water-based polyurethane film B, and drying at 80 ℃ for 2 hours to obtain a water-based polyurethane film A serving as an inner surface; and then, attaching the water-based polyurethane film to the surface of the paper at the temperature of 90 ℃, hot-pressing the water-based polyurethane film to the surface of the paper, and removing the BOPP film to form the low-carbon biodegradable composite film on the surface of the paper, thereby realizing the protection of the paper.
Example 4
The embodiment 4 of the application provides an embodiment of a low-carbon biodegradable composite film, which comprises a preparation step of preparing an aqueous polyurethane A emulsion in the low-carbon biodegradable composite film, a preparation step of an aqueous polyurethane B emulsion and an application process of directly adopting the newly prepared low-carbon biodegradable composite film as a protective layer of a printing pattern on the surface of paper.
The preparation method of the aqueous polyurethane A emulsion comprises the following steps:
after 100g of carbon dioxide polymer glycol with molecular weight of 3000 is dehydrated, 6.8g of 2, 2-dimethylolpropionic acid, 34g of isophorone diisocyanate and 0.3g of stannous octoate catalyst are added to react for 4 hours at 85 ℃, the temperature is reduced to 50-65 ℃, 0.1g of micromolecular chain extender glycol is added to react at 65-75 ℃ until the-NCO content reaches a theoretical value, the temperature is reduced to 40 ℃, acetone is added to adjust the viscosity, then 5.05g of triethylamine is added to react for 15 minutes, 250g of deionized water is added to emulsify for 20 minutes at 0 ℃, then 1.3g of 1, 4-butanediol is added to react for 1 hour, and acetone is removed under reduced pressure to obtain aqueous polyurethane A emulsion.
The preparation method of the aqueous polyurethane B emulsion comprises the following steps:
after dehydration of 100g of carbon dioxide polymer glycol with molecular weight of 2000, adding 8g of 2, 2-dimethylolpropionic acid, 40g of isophorone diisocyanate and 0.2g of stannous octoate catalyst, reacting for 4 hours at 85 ℃, cooling to 50-65 ℃, adding 0.5g of micromolecular chain extender glycol, reacting at 65-75 ℃ until the-NCO content reaches a theoretical value, cooling to 40 ℃, adding acetone to adjust viscosity, then adding 6.03g of triethylamine, reacting for 15 minutes, adding 250g of deionized water, emulsifying for 20 minutes at 0 ℃, then adding 2.11g of ethylenediamine, reacting for 1 hour, and decompressing to remove acetone to obtain aqueous polyurethane B emulsion.
The application process of the biodegradable composite film as the protective layer of the printed pattern on the surface of the paper comprises the following steps:
firstly, coating a BOPP film with a water-based polyurethane emulsion B, drying at 80 ℃ for 2 hours to obtain a water-based polyurethane film B serving as an outer surface, then coating a water-based polyurethane emulsion A on the water-based polyurethane film B, and drying at 80 ℃ for 2 hours to obtain a water-based polyurethane film A serving as an inner surface; and then, attaching the water-based polyurethane film to the surface of the paper at the temperature of 98 ℃, hot-pressing the water-based polyurethane film to the surface of the paper, and removing the BOPP film to form the low-carbon biodegradable composite film on the surface of the paper, thereby realizing the protection of the paper.
The above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should 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 corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. The preparation method of the low-carbon biodegradable composite membrane is characterized by comprising the following steps:
step S1, coating aqueous polyurethane B emulsion on the surface of a template, and drying the aqueous polyurethane B emulsion to obtain an aqueous polyurethane film B;
s2, coating aqueous polyurethane A emulsion on the surface of the aqueous polyurethane film B, drying the aqueous polyurethane A emulsion, and removing a template to obtain a low-carbon biodegradable composite film;
the preparation method of the aqueous polyurethane A emulsion comprises the following steps: the preparation method comprises the steps of carrying out prepolymerization reaction on carbon dioxide polymer polyol, a hydrophilic chain extender and isocyanate, and then sequentially carrying out salification reaction, emulsification reaction, adding a small molecule chain extender and chain extension reaction to obtain the polyurethane polymer;
the preparation method of the aqueous polyurethane B emulsion comprises the following steps: the preparation method comprises the steps of carrying out prepolymerization reaction on carbon dioxide polymer polyol, a hydrophilic chain extender and isocyanate, sequentially carrying out salification reaction, emulsification reaction and chain extension reaction by adding a chain extender.
2. The method for preparing a low-carbon biodegradable composite membrane according to claim 1, wherein the small molecule chain extender is at least one selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 4-butanediol, and 1, 6-hexanediol.
3. The method for preparing a low-carbon biodegradable composite membrane according to claim 1, wherein the chain-extending crosslinking agent is at least one selected from ethylenediamine, propylenediamine and butylenediamine.
4. The method for preparing a low-carbon biodegradable composite membrane according to claim 1, wherein the hydrophilic chain extender is at least one selected from the group consisting of N, N-dihydroxyethyl monomaleamic acid, dimethylolpropionic acid, dimethylolbutyric acid, N- (2-hydroxyethyl) -2-aminoethanesulfonic acid, N- (2-aminoethyl) -2-aminopropanesulfonic acid;
the isocyanate is at least one selected from toluene diisocyanate TDI, hydrogenated diphenylmethane diisocyanate HMDI, isophorone diisocyanate IPDI and hexamethylene diisocyanate HDI;
the catalyst used in the prepolymerization reaction is stannous octoate;
the salifying agent used in the salifying reaction is at least one of triethylamine, tripropylamine, tributylamine, sodium hydroxide and potassium hydroxide;
the solvent used in the emulsification reaction is water.
5. The method for preparing a low-carbon biodegradable composite membrane according to claim 1, wherein in the step S1, the drying temperature is 60-80 ℃ and the time is 0.5-4 hours;
in the step S2, the drying temperature is 40-70 ℃ and the drying time is 0.5-4 h.
6. The method for preparing the low-carbon biodegradable composite membrane according to claim 1, wherein the temperature of the prepolymerization reaction is 40-100 ℃ and the time is 0.5-4 hours;
the temperature of the salification reaction is 20-40 ℃ and the time is 0.1-1 h;
the temperature of the emulsification reaction is-20-0 ℃ and the time is 0.1-1 h;
the temperature of the chain extension reaction is-20-0 ℃ and the time is 0.1-1 h.
7. The low-carbon biodegradable composite film is characterized by comprising an inner surface aqueous polyurethane film A and an outer surface aqueous polyurethane film B;
the aqueous polyurethane film A is obtained by drying the aqueous polyurethane A emulsion according to any one of claims 1-6 to form a film;
the aqueous polyurethane film B is obtained by drying the aqueous polyurethane B emulsion according to any one of claims 1 to 6 to form a film.
8. The low-carbon biodegradable composite film according to claim 7, wherein the thickness of the aqueous polyurethane film a is 5-50 μm;
the thickness of the aqueous polyurethane film B is 5-50 mu m.
9. The application of the low-carbon biodegradable composite film prepared by the preparation method of any one of claims 1-6 in the field of paper surface printing pattern protection.
10. The use of a low-carbon biodegradable composite film according to claim 9 in the field of protection of printed patterns on paper surfaces, characterized in that it comprises in particular: and covering the water-based polyurethane film A on the surface of the printing pattern of the paper, and hot-pressing one side of the water-based polyurethane film B to form a low-carbon biodegradable composite film protective layer on the surface of the printing pattern.
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