CN114806433B - Preparation method of bio-based PU (polyurethane) lettering film and bio-based PU lettering film - Google Patents
Preparation method of bio-based PU (polyurethane) lettering film and bio-based PU lettering film Download PDFInfo
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- CN114806433B CN114806433B CN202210333671.4A CN202210333671A CN114806433B CN 114806433 B CN114806433 B CN 114806433B CN 202210333671 A CN202210333671 A CN 202210333671A CN 114806433 B CN114806433 B CN 114806433B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000004814 polyurethane Substances 0.000 title description 88
- 229920002635 polyurethane Polymers 0.000 title description 3
- 239000004359 castor oil Substances 0.000 claims abstract description 37
- 235000019438 castor oil Nutrition 0.000 claims abstract description 37
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 37
- 108010016626 Dipeptides Proteins 0.000 claims abstract description 30
- 239000004831 Hot glue Substances 0.000 claims abstract description 30
- 239000004970 Chain extender Substances 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 18
- 150000002148 esters Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- 229920005862 polyol Polymers 0.000 claims description 32
- 150000003077 polyols Chemical class 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 17
- 150000003384 small molecules Chemical group 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 14
- 230000001804 emulsifying effect Effects 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 230000003472 neutralizing effect Effects 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- MTCFGRXMJLQNBG-REOHCLBHSA-N L-Serine Natural products OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 6
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-Tryptophan Natural products C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 6
- 229940024606 amino acid Drugs 0.000 claims description 6
- 150000001413 amino acids Chemical class 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229960001153 serine Drugs 0.000 claims description 5
- 229960004799 tryptophan Drugs 0.000 claims description 5
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical group CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 3
- KEZMBAQUUXDDDQ-UHFFFAOYSA-N CCC.N=C=O.N=C=O Chemical group CCC.N=C=O.N=C=O KEZMBAQUUXDDDQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 5
- 230000032798 delamination Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- OUYCCCASQSFEME-QMMMGPOBSA-N L-Tyrosine Natural products OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 150000008575 L-amino acids Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 229960004441 tyrosine Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
Abstract
The invention provides a bio-based PU lettering film and a preparation method thereof. The bio-based small molecular chain monomer (cyclic dipeptide) with a rigid structure is used as a chain extender of the PU chain segment, so that the bio-based PU lettering film required by us has thermal stability and mechanical property, and the production mode is simple, convenient and environment-friendly. In addition, the castor oil modified half ester bio-based is adopted as the production raw material of the PU lettering film, the synthesized PU lettering film and the TPU hot melt adhesive film have similar structures, the bonding capability between the TPU hot melt adhesive film and the PU film can be improved, delamination between interfaces of the TPU hot melt adhesive film and the PU film is avoided, the surface modification treatment of the hot melt adhesive film is not needed, the film can be directly coated, the production process is simple and convenient, the efficiency is high, the cost is low, the process is simple, the effect is various, and the manufacturing of complex patterns is not limited.
Description
Technical Field
The invention relates to the field of lettering films, in particular to a bio-based PU lettering film and a preparation method thereof.
Background
In recent years, the exhaustion of petroleum resources has led to the decrease of the yields of petroleum product derivatives year by year, affecting a wide variety of fields including polyurethane manufacturing industry, and in order to cope with energy crisis, research using renewable resources such as cellulose, lignin, vegetable oil, etc. instead of petrochemical raw materials has become a promising and emerging field from the viewpoint of sustainable development.
In the current market, the preparation of thermal transfer PU is generally carried out by using manual screen printing. However, the manual screen printing has the problems of low efficiency, high cost, complex process, single effect and the like. The transfer printing of the mould is greatly limited by the mould itself when the trademark pattern is manufactured, the complex pattern is difficult to manufacture, and the cost is high. In the production process of the lettering film, the hot melt adhesive film is often required to be subjected to surface treatment modification in the film laminating process so as to firmly coat the lettering film, and thus, the cost and the production efficiency are increased.
Therefore, a bio-based PU lettering film and a preparation method thereof are needed to solve the above technical problems.
Disclosure of Invention
The invention provides a bio-based PU lettering film and a preparation method thereof, which reduce the preparation cost of the lettering film by introducing bio-based raw materials so as to solve the problems of low efficiency, high cost, complex process and single effect of lettering film printing in the prior art.
In order to solve the technical problems, the technical scheme of the invention is as follows: a bio-based PU lettering film comprising: a bio-based PU layer and a TPU hot melt adhesive film layer; wherein the content of the biological base can reach 29% -67%.
The invention also provides a preparation method of the bio-based PU lettering film, which comprises the following steps:
a) Adding an internal emulsifier into a bio-based polyol, mixing with binary isocyanate in a reactor, adding a catalyst, and stirring for reaction to obtain a PU prepolymer;
the bio-based polyol is castor oil modified half ester, and is obtained by reacting maleic anhydride and castor oil, the internal emulsifier is dimethylolbutyric acid, the binary isocyanate is dimethylmethane diisocyanate, the catalyst is an organotin catalyst, the stirring speed is 200-220r/min, the reaction time is 3-4h, and the reaction temperature is 75-85 ℃; the mass ratio of the bio-based polyol to the internal emulsifier to the diisocyanate to the catalyst is (35-45): (7-9): (30-40): (1-2);
b) B, adding a bio-based small molecule chain extender into the PU prepolymer in the step a, performing chain extension reaction, adding a neutralizing agent to stir after the reaction is finished, and then dropwise adding deionized water into the reaction solution to emulsify to obtain bio-based PU;
wherein the mass ratio of the bio-based small molecule chain extender to the neutralizer to the deionized water to the bio-based polyol is (3-5): (6-8): 150: (35-45), wherein the bio-based small molecule chain extender is cyclic dipeptide and one of L-amino acid cyclic dipeptide, L-tryptophan cyclic dipeptide and L-serine cyclic dipeptide, the chain extension reaction time is 2-2.5h, the neutralizer is triethylamine, the neutralization time is 30-40min, the emulsifying stirring speed is 1200-1300r/min, and the emulsifying time is 30-40 mm;
c) C, directly coating the bio-based PU prepared in the step b on the TPU hot melt adhesive film by using a coating machine, naturally airing, and then baking to obtain a bio-based PU lettering film; wherein the coating thickness is 100-200 μm; the baking temperature is 60-80 ℃; the baking time was 12 hours.
Preferably, the reaction stirring speed in step a) is 210r/min and the reaction time is 3.5h.
Preferably, in the step b), the emulsifying stirring rotation speed is 1250r/min, and the emulsifying time is 35 mm; the mass ratio of the bio-based small molecule chain extender to the neutralizer to the deionized water to the bio-based polyol is 4:7:150:40.
preferably, the bio-based polyol is a castor oil modified half-ester.
Preferably, the chain extender is a bio-based small molecular chain monomer cyclic dipeptide with a rigid structure.
The invention also provides a preparation method of the castor oil modified half ester, which comprises the following steps:
d) Adding maleic anhydride and castor oil into a reactor, dehydrating for 2 hours at 100 ℃ and minus 0.095MPa, and cooling to 60 ℃ for reaction to obtain an intermediate product; wherein the mass ratio of the maleic anhydride to the castor oil is 1:12;
e) And c, heating the intermediate product in the step a to 78 ℃ for reaction for 6 hours until the acid value detected in the reaction vessel is stable, and obtaining the castor oil modified half ester.
The invention also provides a preparation method of the cyclic dipeptide, which is characterized by comprising the following steps:
f) Dissolving upstream bio-based material amino acid in ethylene glycol to obtain an intermediate solution;
wherein the concentration of the upstream bio-based material amino acid in ethylene glycol is 1:10g/ml; setting the temperature to 190-210 ℃ and the reaction time to 18-22h;
g) And d, mixing and washing the intermediate solution in the step a with ethanol, carrying out suction filtration to obtain a light yellow solid, and then recrystallizing in the ethanol to obtain the cyclic dipeptide.
Preferably, in step f), the temperature is set to 200℃and the reaction time is 20 hours.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts the bio-based small molecular chain monomer (cyclic dipeptide) with a rigid structure as the chain extender of the PU chain segment, so that the bio-based PU lettering film required by us has thermal stability and mechanical property, and the production mode is simple and convenient and environment-friendly. In addition, the castor oil modified half ester bio-based is adopted as the production raw material of the PU lettering film, the synthesized PU lettering film and the TPU hot melt adhesive film have similar structures, the bonding capability between the TPU hot melt adhesive film and the PU film can be improved, delamination between interfaces of the TPU hot melt adhesive film and the PU film is avoided, the surface modification treatment of the hot melt adhesive film is not needed, the film can be directly coated, the production process is simple and convenient, the efficiency is high, the cost is low, the process is simple, the effect is various, and the manufacturing of complex patterns is not limited. Solves the problems of low efficiency, high cost, complex process and single effect of the lettering film printing in the prior art.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments are briefly described below, and the drawings in the following description are only drawings corresponding to some embodiments of the present invention.
FIG. 1 is a flow chart of a method for preparing a bio-based PU lettering film of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only 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.
The words "first," "second," and the like in the terminology of the present invention are used for descriptive purposes only and are not to be construed as indicating or implying relative importance and not as limiting the order of precedence.
The invention provides a bio-based PU lettering film, which comprises the following components: a bio-based PU layer and a TPU hot melt adhesive film layer. Wherein the content of the biological base can reach 29% -67%. Under the same performance dependence, the bio-based raw materials are introduced as much as possible, the dependence on petroleum-based raw materials is reduced, the application field of the bio-based PU is expanded, and the bio-based PU has the characteristics of environmental protection, excellent hand feeling, high mechanical property, water resistance, solvent resistance and the like.
The invention also provides a preparation method of the bio-based PU lettering film, which comprises the following steps:
a) Adding the bio-based polyol into an internal emulsifier, mixing with the binary isocyanate in a reactor, adding a catalyst, and stirring for reaction to obtain the PU prepolymer.
Wherein the internal emulsifier is dimethylolbutyric acid, the binary isocyanate is dimethylmethane diisocyanate, the catalyst is an organotin catalyst, the stirring speed is 200-220r/min, the reaction time is 3-4h, and the reaction temperature is 75-85 ℃. The mass ratio of the bio-based polyol to the internal emulsifier to the diisocyanate to the catalyst is (35-45): (7-9): (30-40): (1-2).
b) And d, adding a bio-based small molecule chain extender into the PU prepolymer in the step a, performing chain extension reaction for 3-5h, namely, after the reaction is finished, increasing the viscosity in the solution to be no longer increased, adding a neutralizing agent for stirring, and then dropwise adding deionized water into the reaction solution for emulsification to obtain the bio-based PU. The bio-based polyol is too high to cause waste, purification is difficult, too low reaction is incomplete, too much catalyst causes waste, too low catalytic reaction is incomplete, too little emulsifier is incomplete for emulsification, too much emulsifier causes waste, and impurity removal is difficult. The mass ratio of the bio-based small molecule chain extender to the bio-based polyol is too high or too low to generate other substances, so that the required target product cannot be obtained. Too much of the neutralizing agent triethylamine can result in too much alkalinity, and too little alkalinity can not result in the desired target molecule.
Wherein the mass ratio of the bio-based small molecule chain extender to the neutralizer to the deionized water to the bio-based polyol is (3-5): (6-8): 150: (35-45), wherein the bio-based micromolecule chain extender is cyclic dipeptide, the chain extension reaction time is 2-2.5h, the neutralizing agent is triethylamine, the neutralizing time is 30-40min, the emulsifying stirring rotating speed is 1200-1300r/min, and the emulsifying time is 30-40 mm.
c) And c, coating the bio-based PU prepared in the step b on the TPU hot melt adhesive film by using a coating machine, naturally airing, and then baking to obtain the bio-based PU lettering film. Wherein the coating thickness is 100-200 μm. The baking temperature is 60-80 ℃. The baking time was 12 hours.
Wherein the bio-based polyol is castor oil modified half ester. The PU lettering film and the TPU hot melt adhesive film synthesized by using the castor oil modified half ester as raw materials have similar structures, can increase the bonding capability between the TPU hot melt adhesive film and the PU film, avoid delamination between interfaces of the TPU hot melt adhesive film and the PU film, do not need surface modification treatment of the hot melt adhesive film, can directly cover the film, and has the advantages of simple and convenient production process, high efficiency, low cost, simple process, various effects and unrestricted manufacturing of complex patterns.
The chain extender is bio-based small molecular chain monomer cyclic dipeptide with rigid structure. The cyclic dipeptide can enable the needed bio-based PU lettering film to have good mechanical properties, and the production process is simple and environment-friendly.
The invention also provides a preparation method of the castor oil modified half ester, which comprises the following steps:
d) Adding maleic anhydride and castor oil into a reactor, dehydrating for 2 hours at 100 ℃ and minus 0.095MPa, and cooling to 60 ℃ for reaction to obtain an intermediate product; wherein the mass ratio of the maleic anhydride to the castor oil is 1:12; in the invention, the excessive polymerization is easy to produce other substances, and the excessive reaction is severe and can cause blackening of the reaction substances; the polymerization reaction cannot be performed at too low a temperature. The negative pressure is favorable for dehydration.
e) And c, heating the intermediate product in the step a to 78 ℃ for reaction for 6 hours until the acid value detected in the reaction vessel is stable, and obtaining the castor oil modified half-ester.
The invention also provides a preparation method of the cyclic dipeptide, which is characterized by comprising the following steps:
f) Dissolving upstream bio-based material amino acid in ethylene glycol to obtain an intermediate solution;
wherein the concentration of the upstream bio-based material amino acid in ethylene glycol is 1:10g/ml; setting the temperature to 190-210 ℃ and the reaction time to 18-22h;
g) And d, mixing and washing the intermediate solution in the step a with ethanol, carrying out suction filtration to obtain a light yellow solid, and then recrystallizing in the ethanol to obtain the cyclic dipeptide.
Meanwhile, with reference to fig. 1, the following describes the manufacturing process of the bio-based PU lettering film in detail:
it should be noted that various embodiments of the present invention are described below in conjunction with examples for further understanding of the present invention, but it should be understood that these descriptions are merely intended to further illustrate features and advantages of the present invention and are not limiting of the claims of the present invention.
Example 1:
(1) The bio-based polyol, namely castor oil modified half ester, adopts castor oil and maleic anhydride as raw materials, and the specific preparation process is as follows:
castor oil is added into a reactor, dehydrated for 2 hours at 100 ℃ and minus 0.095MPa, cooled to 60 ℃, and then the mass ratio is 1: and (12) adding maleic anhydride, stirring until the solid is completely dissolved, heating to 78 ℃ for reaction for 6 hours until the detected acid value is basically stable, and obtaining the bio-based modified half-ester, namely the castor oil modified half-ester. The hydroxyl value of the prepared castor oil modified half ester is 105mgKOH/g, and the acid value is 52.5mgKOH/g;
(2) The bio-based small molecule chain extender adopts L-amino acid cyclic dipeptide, and the specific preparation process is as follows:
adding 1g/10ml solution prepared from L-amino acid and ethylene glycol into a reactor, pumping air in the reactor, introducing nitrogen for protection, and reacting for 20h at 200 ℃ under stirring of a motor; after the reaction is finished, the obtained product is subjected to mixing washing by glycol and ethanol, suction filtration is carried out to obtain a light yellow solid, and then the light yellow solid is recrystallized in ethanol to obtain a white powder solid, namely cyclic dipeptide (L-tyrosine cyclic dipeptide);
(3) The preparation process of the bio-based PU is as follows:
adding an internal emulsifier into a bio-based polyol, mixing with binary isocyanate in a reactor, adding an organotin catalyst, stirring at 80 ℃ for reaction at a stirring speed of 210r/min for 3.5h to obtain a PU prepolymer; and then adding a biological-based micromolecule chain extender into the PU prepolymer for chain extension reaction, adding a neutralizing agent for stirring after the reaction is finished, emulsifying and stirring at the speed of 1250r/min for 35 mm, and then dripping deionized water into the reaction solution for emulsification to obtain the biological-based PU.
The mass ratio of the bio-based polyol to the internal emulsifier to the diisocyanate to the catalyst is 40:8:35:1.5, the mass ratio of the bio-based small molecule chain extender to the bio-based polyol is 4:40, neutralizing agent triethylamine; the mass ratio of the neutralizer, deionized water and the bio-based polyol is 7:150:40.
(4) The preparation process of the bio-based PU lettering film comprises the following steps:
coating the bio-based PU prepared in the second step with the thickness of 100-200 mu m on the TPU hot melt adhesive film by using a coating machine, naturally airing, and then baking to form a bio-based PU transfer coating; the baking temperature is 70 ℃ and the baking time is 12 hours, and finally the bio-based PU lettering film is obtained.
Example 2
(1) The bio-based polyol, namely castor oil modified half ester, adopts castor oil and maleic anhydride as raw materials, and the specific preparation process is as follows:
castor oil is added into a reactor, dehydrated for 2 hours at 100 ℃ and minus 0.095MPa, cooled to 60 ℃, and then the mass ratio is 1: and (12) adding maleic anhydride, stirring until the solid is completely dissolved, heating to 78 ℃ for reaction for 6 hours until the detected acid value is basically stable, and obtaining the bio-based modified half-ester, namely the castor oil modified half-ester. The hydroxyl value of the prepared castor oil modified half ester is 105mgKOH/g, and the acid value is 52.5mgKOH/g;
(2) The bio-based small molecule chain extender adopts L-tryptophan cyclic dipeptide, and the specific preparation process is as follows:
adding 1g/10ml solution prepared from L-tryptophan and ethylene glycol into a reactor, pumping air in the reactor, introducing nitrogen for protection, and reacting for 20 hours at 200 ℃ under stirring of a motor; after the reaction is finished, the obtained product is subjected to mixing washing by glycol and ethanol, suction filtration is carried out to obtain a light yellow solid, and then the light yellow solid is recrystallized in ethanol to obtain a white powder solid, namely cyclic dipeptide (L-tryptophan cyclic dipeptide);
(3) The preparation process of the bio-based PU is as follows:
adding a bio-based polyol, adding an internal emulsifier, mixing with binary isocyanate in a reactor, adding an organotin catalyst, stirring at 75-85 ℃ for reaction at a stirring speed of 220r/min for 4 hours to obtain a PU prepolymer; and then adding a biological-based micromolecule chain extender into the PU prepolymer for chain extension reaction, adding a neutralizing agent for stirring after the reaction is finished, emulsifying and stirring at the speed of 1300r/min for 40 mm, and then dripping deionized water into the reaction solution for emulsification to obtain the biological-based PU.
The mass ratio of the bio-based polyol to the internal emulsifier to the diisocyanate to the catalyst is 45:9:40:2, the mass ratio of the bio-based small molecule chain extender to the bio-based polyol is 5:45, a neutralizing agent triethylamine; the mass ratio of the neutralizer, deionized water and the bio-based polyol is 8:150:45.
(4) The preparation process of the bio-based PU lettering film comprises the following steps:
coating the bio-based PU prepared in the second step with the thickness of 100-200 mu m on the TPU hot melt adhesive film by using a coating machine, naturally airing, and then baking to form a bio-based PU transfer coating; the baking temperature is 80 ℃ and the baking time is 12 hours, and finally the bio-based PU lettering film is obtained.
Example 3
(1) The bio-based polyol, namely castor oil modified half ester, adopts castor oil and maleic anhydride as raw materials, and the specific preparation process is as follows:
castor oil is added into a reactor, dehydrated for 2 hours at 100 ℃ and minus 0.095MPa, cooled to 60 ℃, and then the mass ratio is 1: and (12) adding maleic anhydride, stirring until the solid is completely dissolved, heating to 78 ℃ for reaction for 6 hours until the detected acid value is basically stable, and obtaining the bio-based modified half-ester, namely the castor oil modified half-ester. The hydroxyl value of the prepared castor oil modified half ester is 105mgKOH/g, and the acid value is 52.5mgKOH/g;
(2) The bio-based small molecule chain extender adopts L-serine cyclic dipeptide, and the specific preparation process is as follows:
adding 1g/10ml solution prepared from L-serine and ethylene glycol into a reactor, pumping air in the reactor, introducing nitrogen for protection, and reacting for 20h at 200 ℃ under stirring of a motor; after the reaction is finished, the obtained product is subjected to mixing washing by glycol and ethanol, suction filtration is carried out to obtain a light yellow solid, and then the light yellow solid is recrystallized in ethanol to obtain a white powder solid, namely cyclic dipeptide (L-serine cyclic dipeptide);
(3) The preparation process of the bio-based PU is as follows:
adding a bio-based polyol, adding an internal emulsifier, mixing with binary isocyanate in a reactor, adding an organotin catalyst, stirring at 75-85 ℃ for reaction at a stirring speed of 200r/min for 3 hours to obtain a PU prepolymer; and then adding a biological-based micromolecule chain extender into the PU prepolymer for chain extension reaction, adding a neutralizing agent for stirring after the reaction is finished, emulsifying and stirring at the speed of 1200r/min for 35 mm, and then dripping deionized water into the reaction solution for emulsification to obtain the biological-based PU.
The mass ratio of the bio-based polyol to the internal emulsifier to the diisocyanate to the catalyst is 35:7:30:1, the mass ratio of the bio-based small molecule chain extender to the bio-based polyol is 3:35, neutralizing agent triethylamine; the mass ratio of the neutralizer, deionized water and the bio-based polyol is 6:150:35.
(4) The preparation process of the bio-based PU lettering film comprises the following steps:
coating the bio-based PU prepared in the second step with the thickness of 100-200 mu m on the TPU hot melt adhesive film by using a coating machine, naturally airing, and then baking to form a bio-based PU transfer coating; the baking temperature is 60 ℃ and the baking time is 12 hours, and finally the bio-based PU lettering film is obtained.
The biological-based PU lettering films prepared in example 1, example 2 and example 3 are removed from release paper, and are subjected to mechanical property test by comparing PU lettering films with the same thickness (100 μm) in the market (10 cm multiplied by 10 cm), and the mechanical property of the biological-based PU lettering films is tested by adopting a tensile testing machine according to the standard ISO1184-1983 'determination of the tensile property of plastic films'.
The mechanical properties of the bio-based PU lettering film are as follows:
by contrast, the bio-based PU lettering films prepared in examples 1, 2 and 3 have better mechanical properties than the lettering films on the market, wherein example 1 has the best mechanical properties.
The bio-based PU lettering films prepared in example 1, example 2, example 3 and example 4 were removed from the release paper for water resistance test:
the biological PU lettering films with the thickness of 100 μm and the size of 10cm×10cm in the comparative samples in the market of example 1, example 2, example 3, example 4 and example were respectively taken, immersed in an aqueous medium for 30 days, and then the quality, size, appearance and mechanical properties of the films were measured. The test equipment adopts a constant-temperature water bath kettle, the soaking medium is distilled water, and the water temperature is 40+/-2 ℃. The test results were as follows:
the test results show that the biological PU lettering films obtained in the examples 1, 2 and 3 have no obvious change in appearance and mechanical properties after water resistance test, and the appearance of the comparative samples in the market is slightly changed, so that the mechanical properties are reduced, and the product has good water resistance.
The bio-based PU lettering films prepared in example 1, example 2, example 3, example 4 and the comparative samples on the market were removed from the release paper, and solvent-resistant tetrachloroethylene test was performed according to the "determination of liquid chemical resistance of plastics" specification GB/T11547-2008:
five groups of biological PU lettering films with the thickness of 100 mu m and the size of 10cm multiplied by 10cm are taken, soaked for 7 days under the condition of organic solvent medium, and the change of the appearance and the mechanical property is measured. The test equipment adopts a sealed metal tank, the soaking medium is tetrachloroethylene, and the test temperature is normal temperature. The test results were as follows:
the test results show that the biological PU lettering films obtained in the examples 1, 2 and 3 have no obvious change in appearance and mechanical properties after water resistance test, and the appearance of the comparative samples in the market is slightly changed, so that the mechanical properties are reduced, and the product provided by the invention has good solvent resistance.
The bio-based lettering films prepared in example 1, example 2 and example 3 were compared with the comparative samples on the market for the detection of the bonding strength between the hot melt adhesive film and the PU film, and each product was tested in three groups, and the comparison results were as follows:
the test results show that the hot melt adhesive and PU bonding capability of the biological-based PU lettering films obtained in the embodiment 1, the embodiment 2 and the embodiment 3 are superior to those of a comparison sample, and the hot melt adhesive and PU bonding capability of the biological-based PU lettering film in the embodiment 1 are optimal, so that the product of the invention does not need to carry out surface treatment on the hot melt adhesive film in the production process, and the bonding capability of the hot melt adhesive and PU is greatly improved.
The invention adopts the bio-based small molecular chain monomer (cyclic dipeptide) with a rigid structure as the chain extender of the PU chain segment, so that the bio-based PU lettering film required by us has thermal stability and mechanical property, and the production mode is simple and convenient and environment-friendly. In addition, the castor oil modified half ester bio-based is adopted as the production raw material of the PU lettering film, the synthesized PU lettering film and the TPU hot melt adhesive film have similar structures, the bonding capability between the TPU hot melt adhesive film and the PU film can be improved, delamination between interfaces of the TPU hot melt adhesive film and the PU film is avoided, the surface modification treatment of the hot melt adhesive film is not needed, the film can be directly coated, the production process is simple and convenient, the efficiency is high, the cost is low, the process is simple, the effect is various, and the manufacturing of complex patterns is not limited. Solves the problems of low efficiency, high cost, complex process and single effect of the lettering film printing in the prior art.
In summary, although the present invention has been described in terms of the preferred embodiments, the preferred embodiments are not limited to the above embodiments, and various modifications and changes can be made by one skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention is defined by the appended claims.
Claims (7)
1. The preparation method of the bio-based PU lettering film is characterized by comprising the following steps of:
a) Adding an internal emulsifier into a bio-based polyol, mixing with binary isocyanate in a reactor, adding a catalyst, and stirring for reaction to obtain a PU prepolymer;
the bio-based polyol is castor oil modified half ester, and is obtained by reacting maleic anhydride and castor oil, the internal emulsifier is dimethylolbutyric acid, the binary isocyanate is dimethylmethane diisocyanate, the catalyst is an organotin catalyst, the stirring speed is 200-220r/min, the reaction time is 3-4h, and the reaction temperature is 75-85 ℃; the mass ratio of the bio-based polyol to the internal emulsifier to the diisocyanate to the catalyst is (35-45): (7-9): (30-40): (1-2);
b) B, adding a bio-based small molecule chain extender into the PU prepolymer in the step a, performing chain extension reaction, adding a neutralizing agent to stir after the reaction is finished, and then dropwise adding deionized water into the reaction solution to emulsify to obtain bio-based PU;
wherein the mass ratio of the bio-based small molecule chain extender to the neutralizer to the deionized water to the bio-based polyol is (3-5): (6-8): 150: (35-45), wherein the bio-based small molecule chain extender is cyclic dipeptide and one of L-amino acid cyclic dipeptide, L-tryptophan cyclic dipeptide and L-serine cyclic dipeptide, the chain extension reaction time is 2-2.5h, the neutralizer is triethylamine, the neutralization time is 30-40min, the emulsifying stirring speed is 1200-1300r/min, and the emulsifying time is 30-40 mm;
c) C, directly coating the bio-based PU prepared in the step b on the TPU hot melt adhesive film by using a coating machine, naturally airing, and then baking to obtain a bio-based PU lettering film; wherein the coating thickness is 100-200 μm; the baking temperature is 60-80 ℃; the baking time was 12 hours.
2. The method according to claim 1, wherein the reaction stirring speed in the step a) is 210r/min and the reaction time is 3.5h.
3. The method according to claim 1, wherein in the step b), the emulsifying stirring speed is 1250r/min, and the emulsifying time is 35 mm; the mass ratio of the bio-based small molecule chain extender to the neutralizer to the deionized water to the bio-based polyol is 4:7:150:40.
4. the preparation method of the castor oil modified half ester according to claim 1, comprising the following steps:
d) Adding maleic anhydride and castor oil into a reactor, dehydrating for 2 hours at 100 ℃ and minus 0.095MPa, and cooling to 60 ℃ for reaction to obtain an intermediate product; wherein the mass ratio of the maleic anhydride to the castor oil is 1:12;
e) And c, heating the intermediate product in the step a to 78 ℃ for reaction for 6 hours until the acid value detected in the reaction vessel is stable, and obtaining the castor oil modified half ester.
5. The method of claim 1, wherein the method of producing the cyclic dipeptide comprises the steps of:
f) Dissolving upstream bio-based material amino acid in ethylene glycol to obtain an intermediate solution;
wherein the concentration of the upstream bio-based material amino acid in ethylene glycol is 1:10g/ml; setting the temperature to 190-210 ℃ and the reaction time to 18-22h;
g) And d, mixing and washing the intermediate solution in the step a with ethanol, carrying out suction filtration to obtain a light yellow solid, and then recrystallizing in the ethanol to obtain the cyclic dipeptide.
6. The method according to claim 5, wherein in the step f), the temperature is set to 200℃and the reaction time is set to 20 hours.
7. A bio-based PU lettering film, characterized in that it is produced using the method for producing a bio-based PU lettering film according to any one of claims 1 to 6.
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