CN116462967A - Transparent flame-retardant Gao Wenlei-carving-resistant identification product and preparation method thereof - Google Patents
Transparent flame-retardant Gao Wenlei-carving-resistant identification product and preparation method thereof Download PDFInfo
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- CN116462967A CN116462967A CN202310459785.8A CN202310459785A CN116462967A CN 116462967 A CN116462967 A CN 116462967A CN 202310459785 A CN202310459785 A CN 202310459785A CN 116462967 A CN116462967 A CN 116462967A
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000003063 flame retardant Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 9
- 229920001721 polyimide Polymers 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 23
- 239000009719 polyimide resin Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004642 Polyimide Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 230000000865 phosphorylative effect Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000010329 laser etching Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000010147 laser engraving Methods 0.000 abstract description 22
- 238000005516 engineering process Methods 0.000 abstract description 14
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 abstract description 2
- 239000012459 cleaning agent Substances 0.000 abstract description 2
- 230000004907 flux Effects 0.000 abstract description 2
- 238000005476 soldering Methods 0.000 abstract description 2
- 230000000007 visual effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002585 base Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
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Abstract
The invention relates to a transparent flame-retardant Gao Wenlei carving-resistant marking product and a preparation method thereof, and belongs to the technical field of high polymer materials. The preparation technology of the flexible laser carving identification product provided by the invention does not need to add any other auxiliary agents such as laser carving auxiliary agents, so that the production efficiency can be effectively improved, and the production cost can be saved; the laser engraving identification product obtained by the preparation technology of the flexible laser engraving identification product provided by the invention has high transparency and can be applied to the field of visual intelligent electronics; the laser carving mark product obtained by the preparation technology of the flexible laser carving mark product provided by the invention can resist the corrosion of various soldering flux, cleaning agent and other chemical substances at the temperature of 300 ℃, and simultaneously ensure that the excellent performance is maintained under various extreme environments such as high temperature, abrasion and the like; the limiting oxygen index of the laser engraving identification product obtained by the preparation technology of the flexible laser engraving identification product provided by the invention is up to 43%, and the flexible laser engraving identification product can be used as a flame retardant material.
Description
Technical Field
The invention relates to a transparent flame-retardant Gao Wenlei carving-resistant marking product and a preparation method thereof, and belongs to the technical field of high polymer materials.
Background
At present, the traceability of commodity information not only provides corresponding awareness rights and options for consumers, but also is beneficial to quality management of enterprises. The key to realizing commodity information tracking is to enable commodities to have stable identifications. At present, an ink printing mode is generally adopted to obtain the identification pattern, but the ink printing identification pattern is easy to fade and even fall off along with the time, and the identification function is lost. In addition, the use of ink chemicals can also present environmental concerns.
The laser carving marking technology is a technology for carrying out surface treatment by using an optical principle, and has the advantages of permanence, high processing efficiency and the like compared with the traditional ink-jet printing, so that the laser carving marking technology is greatly popularized. At present, polymer substrates used for laser engraving marking are mainly traditional high polymer materials such as Polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene terephthalate (PET) and the like. In the molding processing process of the material, a large amount of other auxiliary agents such as laser engraving powder are required to be added, which is not beneficial to continuous production of products and improves the production cost. On the other hand, identification products based on these conventional polymeric substrates are difficult to apply under extreme conditions of high temperature, acid-base corrosion, etc. Therefore, the project aims to develop a high-stability laser engraving identification product, and meets the application requirements in complex and changeable environments.
In view of the above-mentioned drawbacks, the present invention is to create a transparent flame-retardant Gao Wenlei carving-resistant logo product and a preparation method thereof, which make the product have industrial application value.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation technology of a transparent flame-retardant Gao Wenlei-carving-resistant identification product.
A second object of the present invention is to provide a polyimide substrate for a transparent flame retardant Gao Wenlei engraving resistant signage article.
A third object of the present invention is to provide a method for producing the polyimide.
The transparent flame-retardant Gao Wenlei carving-resistant identification product provided by the invention has the advantages that the base material of the transparent flame-retardant Gao Wenlei carving-resistant identification product is transparent, soluble and fusible polyimide.
Further, the structural formula of the transparent soluble and fusible polyimide is shown as (1):
wherein x+y=1 and 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1.
Further, the preparation method of the transparent soluble and fusible polyimide comprises the following steps:
firstly, diamine monomer, compatibilizer, fatty chain-containing diacid monomer and phosphorylating agent are dissolved in solvent, after the first-stage reaction is carried out by slowly heating up under nitrogen atmosphere, aromatic diacid monomer is added for the second-stage reaction, after the reaction is finished, the mixture is poured into methanol for precipitation, and the polyimide resin is obtained by filtering and drying.
Further, the structural formula of the diamine monomer is shown as (2):
the structural formula of the fatty chain-containing diacid monomer is shown as (3):
the structural formula of the aromatic diacid monomer is shown as (4):
further, the mole ratio of the fatty chain-containing diacid monomer to the aromatic diacid monomer is 0:1-1:0; the molar ratio of the sum of the mole numbers of the fatty chain-containing diacid monomer and the aromatic diacid monomer to the diamine monomer is 0.8-1.2.
Further, the reaction temperature in the first stage is 70-120 ℃ and the reaction time is 5-10 h; the reaction temperature of the second stage is 90-140 ℃ and the reaction time is 8-24 h.
Further, the compatibilizer is calcium chloride or lithium chloride or a mixture of calcium chloride and lithium chloride.
Further, the phosphorylating reagent is triphenyl phosphite, and the solvent is N-methyl pyrrolidone.
A preparation method of a transparent flame-retardant Gao Wenlei carving mark product comprises the following specific preparation steps:
after forming a film of transparent soluble and fusible polyimide resin, carrying out laser etching, wherein the laser wavelength is 600-1064 nm; the distance between the laser lines is 10-100 mu m; the laser power is 1-20 mW.
Further, the laser wavelength is 780nm; the laser line spacing is 50 μm; the laser power is 10mW.
By means of the scheme, the invention has at least the following advantages:
according to the preparation technology of the flexible laser carving identification product, the base material is specially made polyimide, the laser absorption capacity of the base material is extremely strong, the base material is high-temperature-resistant and corrosion-resistant, the flame retardance is good, no other auxiliary agents such as laser carving auxiliary agents are needed, the production efficiency can be effectively improved, and the production cost is saved; the laser engraving identification product obtained by the preparation technology of the flexible laser engraving identification product provided by the invention has high transparency and can be applied to the field of visual intelligent electronics; the laser carving mark product obtained by the preparation technology of the flexible laser carving mark product provided by the invention can resist the corrosion of various soldering flux, cleaning agent and other chemical substances at the temperature of 300 ℃, and simultaneously ensure that the excellent performance is maintained under various extreme environments such as high temperature, abrasion and the like; the limiting oxygen index of the laser engraving identification product obtained by the preparation technology of the flexible laser engraving identification product provided by the invention is up to 43%, and the flexible laser engraving identification product can be used as a flame retardant material.
The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate a certain embodiment of the present invention and therefore should not be considered as limiting the scope, and that other related drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a photograph of a flexible laser engraving identification article obtained in example 1.
FIG. 2 is an ultraviolet absorption spectrum of the polyimide resin synthesized in example 1.
Fig. 3 is a phase change analysis spectrum of the polyimide resin synthesized in example 1.
FIG. 4 is a thermogravimetric analysis spectrum of the polyimide resin synthesized in example 1.
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The base material used for preparing the transparent flame-retardant Gao Wenlei carving-resistant marking product is transparent soluble polyimide, and the structural formula is shown as follows:
wherein x+y=1 and 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1;
the invention provides a preparation method of soluble and fusible polyimide resin, which comprises the following steps:
the molar ratio is 0 to 1:1 (preferably 0.4:1) and a diamine monomer (compound 1) under nitrogen atmosphere, slowly heating to 70-120 ℃ (preferably 90 ℃), reacting for 5-10 h (preferably 7 h), and performing a first-stage reaction; then, the molar ratio with respect to compound 2 is added in the range from 0 to 1:1 (preferably 0.6:1) and reacting at 90-140 ℃ (preferably 110 ℃) for 8-24 hours (preferably 12 hours). After the reaction is finished, pouring the mixture into methanol for precipitation, filtering and drying to obtain the transparent soluble fusible polyimide resin.
The compatibilizer is calcium chloride or lithium chloride or a mixture of calcium chloride and lithium chloride (preferably a mixture of calcium chloride and lithium chloride with a molar ratio of 1:1).
The phosphorylating agent is triphenyl phosphite (TPP); the solvent is N-methyl pyrrolidone.
The invention provides a preparation technology of a flexible laser carving identification product, wherein the laser wavelength of the preparation of the flexible transparent flame-retardant Gao Wenlei carving identification product is 600-1064 nm (preferably 780 nm); the laser line pitch is 10 to 100 μm (preferably 50 μm); the laser power is 1-20 mW (preferably 10 mW).
Example 1
The embodiment provides a preparation technology for preparing a transparent flame-retardant Gao Wenlei carving-resistant identification product, which comprises the following steps:
(1) The substrate used was polyimide having the following repeating structural units.
Wherein x+y=1 and 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1.
A preparation method of polyimide resin comprises the following steps:
the molar ratio is 0 to 4:1, slowly heating the compound 1 and the compound 2 to 90 ℃ in a nitrogen atmosphere, reacting for 7 hours, and carrying out a first-stage reaction; then, compound 3 was added in a molar ratio of 0.6:1 relative to compound 2. After the reaction is finished, pouring the mixture into methanol for precipitation, filtering and drying to obtain the transparent soluble fusible polyimide resin.
(2) After the polyimide resin obtained in the step 1 is formed into a film, laser etching is carried out, and the laser wavelength is 780nm; the laser line spacing is 50 μm; the laser power was 6mW.
Example 2
The only difference between this example and example 1 is that the molar ratio of compound 1 to compound 3 was 0.1:0.9 in the synthesis of the polyimide resin.
Example 3
The only difference between this example and example 1 is that the molar ratio of compound 1 to compound 3 was 0.9:0.1 in the synthesis of the polyimide resin.
Comparative example 1
This comparative example differs from example 1 in that the substrate used for the flexible laser engraving identification article is a PC resin.
Comparative example 2
This comparative example differs from example 1 in the structure of the polyimide resin used for the flexible laser engraving identification article substrate is:
the following performance tests were conducted on the transparent polyimide resin prepared in example 1, and the test results are shown in table 1:
optical transmittance: the optical transmittance is tested by an UltraScan PRO full-automatic color difference meter, the wavelength is selected to be 375-1000 nm, and the thickness of the film is 50 mu m.
Thermal stability test: the thermal stability test was performed on a TGA 4000 thermogravimetric analyzer from PerkinElmer, usa. Specific parameter setting: sample mass: 40.2mg; test temperature: 30-800 ℃; rate of temperature rise: 10 ℃/min; test environment: and (3) nitrogen atmosphere.
Phase change test: the phase transition test uses DMA 8000 from PE in the united states. Specific parameter setting: setting frequency: 1Hz; test temperature: 30-500 ℃; rate of temperature rise: 5 ℃/min.
Specifically, as shown in fig. 2, 3 and 4, fig. 2 is an ultraviolet absorption spectrum of the polyimide resin synthesized in example 1. Fig. 3 is a phase change analysis spectrum of the polyimide resin synthesized in example 1. FIG. 4 is a thermogravimetric analysis spectrum of the polyimide resin synthesized in example 1.
TABLE 1
As shown in Table 1, the polyimide resin prepared by the method has good optical transparency, higher glass transition temperature, excellent thermal stability and higher limiting oxygen index, and can meet the application in the aspects of transparency, high temperature and flame retardance.
The following performance tests were performed on examples 1-3 and comparative examples 1-2, and the results are shown in Table 2:
high temperature resistance test: the laser engraving products prepared in examples 1-3 and comparative examples 1-2 were placed on a heated table and heated at 200℃for half an hour to verify that the marking properties were lost.
Acid resistance test: after the laser engraving products prepared in examples 1 to 3 and comparative examples 1 to 2 were completely immersed in an acid solution having a pH of 2 prepared by hydrochloric acid for 6 hours, they were taken out and dried to verify whether the marking property was lost. .
Alkali resistance test: after the laser engraving products prepared in examples 1 to 3 and comparative examples 1 to 2 were completely immersed in an acid solution having a pH of 12 prepared by hydrochloric acid for 6 hours, they were taken out and dried to verify whether the marking property was lost.
TABLE 2
As can be seen from examples 1-3 and comparative example 1, comparative example 1 has good optical transparency, but cannot be used in high-temperature and acid-base environments, and the flexible laser engraving product prepared by the method can be used in high-temperature and acid-base environments. As can be seen from examples 1-3 and comparative example 2, comparative example 2 has poor optical transparency although it can be used in high temperature and acid-base environments, and the flexible laser engraving product prepared in the application has good optical transparency.
In conclusion, the flexible laser engraving product prepared by the method has excellent comprehensive performance, good optical transparency and can be applied to complex environments such as high temperature, acid and alkali.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and it should be noted that it is possible for those skilled in the art to make several improvements and modifications without departing from the technical principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.
Claims (10)
1. A transparent flame retardant Gao Wenlei engraving resistant logo product, characterized in that: the base material of the transparent flame-retardant Gao Wenlei carving mark product is transparent soluble and fusible polyimide.
2. A transparent flame retardant Gao Wenlei engraving resistant signage article as defined in claim 1, wherein: the structural formula of the transparent soluble and fusible polyimide is shown as (1):
wherein x+y=1 and 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1.
3. A transparent flame retardant Gao Wenlei engraving resistant signage article as defined in claim 1 or 2, wherein: the preparation method of the transparent soluble and fusible polyimide comprises the following steps:
firstly, diamine monomer, compatibilizer, fatty chain-containing diacid monomer and phosphorylating agent are dissolved in solvent, after the first-stage reaction is carried out by slowly heating up under nitrogen atmosphere, aromatic diacid monomer is added for the second-stage reaction, after the reaction is finished, the mixture is poured into methanol for precipitation, and the polyimide resin is obtained by filtering and drying.
4. A transparent flame retardant Gao Wenlei engraving resistant signage article as defined in claim 3, wherein: the structural formula of the diamine monomer is shown as (2):
the structural formula of the fatty chain-containing diacid monomer is shown as (3):
the structural formula of the aromatic diacid monomer is shown as (4):
5. a transparent flame retardant Gao Wenlei engraving resistant signage article as defined in claim 3, wherein: the mol ratio of the fatty chain-containing diacid monomer to the aromatic diacid monomer is 0:1-1:0; the molar ratio of the sum of the mole numbers of the fatty chain-containing diacid monomer and the aromatic diacid monomer to the diamine monomer is 0.8-1.2.
6. A transparent flame retardant Gao Wenlei engraving resistant signage article as defined in claim 3, wherein: the reaction temperature in the first stage is 70-120 ℃ and the reaction time is 5-10 h; the reaction temperature of the second stage is 90-140 ℃ and the reaction time is 8-24 h.
7. A transparent flame retardant Gao Wenlei engraving resistant signage article as defined in claim 3, wherein: the compatibilizer is calcium chloride or lithium chloride or a mixture of calcium chloride and lithium chloride.
8. A transparent flame retardant Gao Wenlei engraving resistant signage article as defined in claim 3, wherein: the phosphorylating reagent is triphenyl phosphite, and the solvent is N-methyl pyrrolidone.
9. The method for preparing the transparent flame-retardant Gao Wenlei carving-resistant marking product as claimed in claim 1, which is characterized by comprising the following specific preparation steps:
after forming a film of transparent soluble and fusible polyimide resin, carrying out laser etching, wherein the laser wavelength is 600-1064 nm; the distance between the laser lines is 10-100 mu m; the laser power is 1-20 mW.
10. The method for preparing the transparent flame-retardant Gao Wenlei engraving resistant marking product according to claim 9, which is characterized in that: the laser wavelength is 780nm; the laser line spacing is 50 μm; the laser power is 10mW.
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