CN115340783B - Optical fiber coating adhesion promoter and preparation method thereof - Google Patents
Optical fiber coating adhesion promoter and preparation method thereof Download PDFInfo
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- CN115340783B CN115340783B CN202211057564.XA CN202211057564A CN115340783B CN 115340783 B CN115340783 B CN 115340783B CN 202211057564 A CN202211057564 A CN 202211057564A CN 115340783 B CN115340783 B CN 115340783B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
The invention provides an optical fiber coating adhesion promoter and a preparation method thereof, wherein the optical fiber coating adhesion promoter has a structure shown in a general formula, wherein R is as follows 1 Is of diisocyanate structure, R 2 Is of a hydroxy acrylic ester structure, R 3 Is silane coupling agent with amino group, R 4 Is of a triisocyanate structure. The adhesion promoter disclosed by the invention has good compatibility with the optical fiber coating, has no phenomena of turbidity, layering and the like, has almost no influence on the mechanical property and viscosity of the optical fiber coating by adding the adhesion promoter, and can greatly improve the adhesion between the bare optical fiber and the coating by only adding a small amount of the adhesion promoter, so that the reliability of the optical fiber is greatly improved.
Description
Technical Field
The invention relates to the technical field of optical fiber coating, in particular to an optical fiber coating adhesion promoter and a preparation method thereof.
Background
Optical fibers are usually fiber materials drawn from glass or plastic and have the characteristics of thin, brittle and easy damage, so that multilayer coating is required to be coated on the surface of the bare optical fiber, thereby protecting the bare optical fiber and imparting excellent mechanical properties to the optical fiber. The general optical fiber is provided with two coating layers, and the inner coating layer is in direct contact with the optical fiber and has lower modulus so as to ensure that the optical fiber is not easy to damage; the outer coating layer requires a higher modulus to ensure that the fiber is not damaged by external forces.
The optical fiber coating is mainly an ultraviolet light solidified acrylic resin formula system with a free radical polymerization mechanism, and the system coating mainly forms acting force with the bare optical fiber by physical acting force such as hydrogen bond and the like, thereby being coated on the surface of the optical fiber. The acting force formed by the hydrogen bond is weaker, and in the use process of the optical fiber, the coating layer can be dropped off, so that the service life of the optical fiber is influenced. It is therefore important to add adhesion promoters to optical fiber coatings.
Chinese patent CN 104449023B discloses an adhesion promoter with carbon-carbon double bond and carboxyl as active groups, in which the reaction temperature is up to 140 ℃, the danger coefficient is large during the expansion production, and the industrial application is greatly limited. Chinese patent CN 102167925A discloses an aqueous adhesion promoter for optical fiber coating, but most of the optical fiber coatings currently sold in the market are oil coatings, which limits the application range of the adhesion promoter. The conventional optical fiber coating adhesion promoter mainly comprises silane coupling agents such as KH550, KH560, KH570 and the like, wherein the silane coupling agents have low molecular weight, are easy to volatilize, are unstable and are easy to hydrolyze, and are added into an optical fiber coating system, so that the influence on the viscosity of the coating is large, and the addition amount of the silane coupling agents is limited.
Therefore, the invention aims to provide the optical fiber coating adhesion promoter which is simple in synthesis process, controllable in production process cost and good in adhesion promoting effect, and the preparation method thereof.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides an optical fiber coating adhesion promoter and a preparation method thereof.
The invention provides an optical fiber coating adhesion promoter, which has a structure shown in the following general formula:
wherein R is 1 Is of diisocyanate structure, R 2 Is of a hydroxy acrylic ester structure, R 3 Is silane coupling agent with amino group, R 4 Is of a triisocyanate structure.
The acrylate coating is in contact with the bare optical fiber, and only physical acting forces such as hydrogen bonds are used for bonding the bare optical fiber, so that the bonding force is poor. After the adhesion promoter is added, in the process of optical fiber drawing technology, double bonds in the adhesion promoter and acrylic ester undergo addition reaction to bond, and the silicon alkoxy in the adhesion promoter reacts with hydroxyl on the surface of glass to form a chemical bond. Therefore, the adhesion promoter serves as a tie to link the optical fiber coating with the bare optical fiber through chemical bonds, thereby enhancing the adhesion.
The adhesion promoter is light yellow transparent viscous liquid, is added into the optical fiber coating, has good compatibility, and can greatly improve the adhesion between the bare optical fiber and the coating.
According to the optical fiber coating adhesion promoter provided by the invention, R 1 Is isophorone diisocyanate IPDI, toluene diisocyanate TDI, diphenylmethane diisocyanateEster MDI, methylenebis (4-cyclohexyl isocyanate) or 1, 6-hexane diisocyanate HDI.
According to the optical fiber coating adhesion promoter provided by the invention, R 3 Is gamma-aminopropyl triethoxysilane KH550, N-beta- (aminoethyl) -gamma-aminopropyl trimethylethoxysilane KH792 or N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane DL602.
According to the optical fiber coating adhesion promoter provided by the invention, R 2 Is hydroxypropyl acrylate, hydroxypropyl methacrylate, 2-hydroxybutyl (meth) acrylate or hydroxyethyl methacrylate.
According to the optical fiber coating adhesion promoter provided by the invention, R 4 Is MDI trimer, TDI trimer, HDI trimer or HDI biuret.
The invention also provides a preparation method of the optical fiber coating adhesion promoter, which comprises the following steps:
(1) Preparation of an intermediate product bearing both siloxy and isocyanate groups
Mixing the silane coupling agent with amino group with diisocyanate or triisocyanate under nitrogen atmosphere, and stirring for 1-5 h at 10-25 ℃ to prepare an intermediate product with both siloxy groups and isocyanate groups;
(2) Capping to obtain the crude product of the adhesion promoter
Mixing the end capping agent hydroxyacrylate, the catalyst and the intermediate product prepared in the step (1), heating to 40-80 ℃, and reacting for 4-8 h to obtain the crude product of the adhesion promoter.
The preparation method provided by the invention has the advantages of simple process operation, good repeatability and controllability, controllable production cost and no use of organic solvents. Wherein, the silane coupling agent with amino and R in the general formula 3 Corresponding to diisocyanate and R 1 Corresponding to the triisocyanate and R 4 Corresponding to the hydroxy acrylic ester and R 2 Corresponding to the above.
According to the preparation method provided by the invention, in the step (1), the mass ratio of amino groups to isocyanate groups is 1:1.8-2.2.
According to the preparation method provided by the invention, in the step (1), the silane coupling agent with amino is dropwise added into diisocyanate or triisocyanate for mixing.
According to the preparation method provided by the invention, in the step (2), the mass ratio of the hydroxy acrylic ester to the isocyanate group is 1:1.8-2.2.
According to the preparation method provided by the invention, in the step (2), the catalyst is dibutyl tin dilaurate or n-butyl titanate, and the addition amount is 0.1-2wt.% of the total reactants.
According to the preparation method provided by the invention, the preparation method further comprises the step of refining the crude product obtained in the step (2), wherein the refining is carried out by carrying out reduced pressure distillation on the crude product at 60-70 ℃.
Further, the pressure of the reduced pressure distillation is-0.096 Mpa to 0.09Mpa.
When the adhesion promoter for the optical fiber coating is used, the adhesion promoter is added into the optical fiber coating and uniformly mixed. Preferably, the optical fiber coating adhesion promoter is added in an amount of 1 to 5wt.% of the optical fiber coating.
The invention provides an adhesive force promoter for optical fiber coating and a preparation method thereof, the adhesive force promoter has better compatibility with the optical fiber coating, has no phenomena of turbidity, layering and the like, has almost no influence on the mechanical properties of the optical fiber coating by adding the adhesive force promoter, can greatly improve the adhesive force between bare optical fibers and the coating by only adding a small amount of the adhesive force promoter, and greatly improves the reliability of the optical fibers.
Drawings
FIG. 1 is a schematic diagram of the operation of the present invention for testing the pullout force of an optical fiber.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides an optical fiber coating adhesion promoter, which has the following structural formula:
the preparation method comprises the following steps:
(1) 66.6g of isophorone diisocyanate was charged into a 250ml four-necked flask equipped with a heating, magnetic stirring and temperature controller under nitrogen atmosphere, and 66.3g of gamma-aminopropyl triethoxysilane was dropwise added at a rate of 1 drop/sec through a constant pressure dropping funnel at 20℃and stirred for 5 hours, during which the conversion of isocyanate groups was measured.
(2) After the isocyanate group content is stabilized, 42g of hydroxypropyl acrylate and 0.8g of dibutyltin dilaurate are taken and mixed with the product of the step (1), the temperature is raised to 60 ℃, the mixture is stirred and reacted for 8 hours, the conversion rate of the isocyanate group is measured, and when the isocyanate group content is less than 0.1wt.%, the reaction is determined to be completed.
(3) And removing low-boiling-point substances in the system from the product at 70 ℃ per-0.096 MPa, so as to prepare the pale yellow transparent optical fiber coating adhesion promoter AP1.
The prepared adhesion promoter AP1 is respectively added into optical fiber inner layer paint A, B (paint A, B is respectively provided by two different merchants, polyurethane acrylic ester is taken as a main component, acrylic ester monomers are taken as solvents) of an acrylic ester system, uniformly stirred, subjected to standing and defoaming, and subjected to mechanical property test, adhesion test and viscosity test, and test results are shown in tables 1 and 2.
Example 2
The embodiment provides an optical fiber coating adhesion promoter, which has the following structural formula:
the preparation method comprises the following steps:
(1) 51g of HDI biuret was introduced into a 250ml four-necked flask equipped with a heating, magnetic stirring and temperature controller under nitrogen atmosphere, 44.2g of gamma-aminopropyl triethoxysilane was added dropwise at a rate of 1 drop/sec through a constant pressure dropping funnel at 25℃and stirred for 5 hours, during which the conversion of isocyanate groups was determined.
(2) 14g of hydroxypropyl acrylate and 0.5g of dibutyltin dilaurate were taken, the temperature was raised to 60℃and the reaction was stirred for 8 hours, during which the conversion of isocyanate groups was measured, and when the isocyanate content was less than 0.1wt.%, the reaction was determined to be complete.
(3) And removing low-boiling-point substances in the system from the product at 70 ℃ per-0.096 MPa, so as to prepare the pale yellow transparent optical fiber coating adhesion promoter AP2.
And respectively adding the adhesion promoter AP2 into the optical fiber inner layer coating A, B of the acrylate system, uniformly stirring, standing for defoaming, and then performing mechanical property test, adhesion test and viscosity test, wherein the test results are shown in tables 1 and 2.
Example 3
The embodiment provides an optical fiber coating adhesion promoter, which has the following structural formula:
the preparation method comprises the following steps:
(1) 66.6g of isophorone diisocyanate was charged into a 250ml four-necked flask equipped with a heating, magnetic stirring and temperature controller under nitrogen atmosphere, and 66.3g of gamma-aminopropyl triethoxysilane was dropwise added at a rate of 1 drop/sec through a constant pressure dropping funnel at 20℃and stirred for 5 hours, during which the conversion of isocyanate groups was measured.
(2) 37.5g of hydroxyethyl acrylate and 0.8g of dibutyltin dilaurate were taken, the temperature was raised to 60 ℃, the reaction was stirred for 8 hours, the conversion of isocyanate groups was measured during the reaction, and when the isocyanate content was less than 0.1wt.%, the reaction was determined to be completed.
(3) And removing low-boiling-point substances in the system from the product at 70 ℃ per-0.096 MPa, so as to prepare the pale yellow transparent optical fiber coating adhesion promoter AP3.
The prepared adhesion promoter AP3 is respectively added into the optical fiber inner layer coating A, B of the acrylate system, stirred uniformly, and subjected to mechanical property test, adhesion test and viscosity test after standing and defoaming, and the test results are shown in tables 1 and 2.
Example 4
The embodiment provides an optical fiber coating adhesion promoter, which has the following structural formula:
the preparation method comprises the following steps:
(1) 66.6g of isophorone diisocyanate was charged into a 250ml four-necked flask equipped with a heating, magnetic stirring and temperature controller under nitrogen atmosphere, and 66.7g of N-. Beta. -aminoethyl-. Gamma. -aminopropyl trimethylethoxysilane KH792 was dropwise added at a rate of 1 drop/sec through a constant pressure dropping funnel at 20℃and stirred for 5 hours, during which the conversion of isocyanate groups was measured.
(2) 42g of hydroxypropyl acrylate and 0.8g of dibutyltin dilaurate were taken, heated to 60℃and stirred for 8 hours, during which the conversion of isocyanate groups was determined and when the isocyanate content was less than 0.1wt.%, the reaction was determined to be complete.
(3) And removing low-boiling substances in the system from the product at 70 ℃ per-0.096 MPa, so as to prepare the pale yellow transparent optical fiber coating adhesion promoter AP4.
The prepared adhesion promoter AP4 is respectively added into the optical fiber inner layer coating A, B of the acrylate system, stirred uniformly, and subjected to mechanical property test, adhesion test and viscosity test after standing and defoaming, and the test results are shown in tables 1 and 2.
Comparative example
Commercially available silane coupling agent KH570 is directly added into the paint A, B, the addition amounts are respectively 2% and 4%, the mixture is uniformly stirred, and after standing and defoaming, mechanical property test, adhesive force test and viscosity test are carried out, and the test results are shown in Table 1 and Table 2.
Table 1 paint a test
Table 2 coating B test
Remarks: modulus, tensile strength, elongation at break tests were tested with reference to GBT 1040.1-2006, GBT 1040.2-2006, GBT 1040.3-2006, respectively; shear strength test referring to GBT 13936-2014 test, the substrate was tuned to be a glass material. Fiber peel force test the peak value was averaged with reference to GB/T15972.32-2008. Fiber extraction force test referring to YD/T3022.1-2016, the specific operation is as shown in FIG. 1. The method shown in FIG. 1 differs from YD/T3022.1-2016: one end of the fiber was fixed to the substrate with glue and the 3mm coating was removed at 1 cm.
The result shows that after the adhesion promoter prepared by the invention is added, the shearing strength of the optical fiber coating is obviously increased, the stripping force and the pulling force of the drawn optical fiber are obviously improved, the influence on the viscosity of the main coating is small, and the adhesive force modifying agent is suitable for the adhesive force modifying of the existing coating.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (3)
1. An optical fiber coating adhesion promoter is characterized by having the following structural formula:
the optical fiber coating is an oily acrylic ester coating.
2. The method for preparing the adhesion promoter for optical fiber coating according to claim 1, comprising:
(1) Preparation of an intermediate product bearing both siloxy and isocyanate groups
Mixing gamma-aminopropyl triethoxysilane and HDI biuret in nitrogen atmosphere, and stirring for 1-5 h at 10-25 ℃ to prepare an intermediate product with both siloxy and isocyanate groups; wherein the mass ratio of amino groups to isocyanate groups is 1:1.8-2.2; mixing by dripping gamma-aminopropyl triethoxysilane into HDI biuret;
(2) Capping to obtain the crude product of the adhesion promoter
Mixing end capping agent hydroxypropyl acrylate and catalyst dibutyl tin dilaurate with the intermediate product prepared in the step (1), heating to 40-80 ℃, and reacting for 4-8 hours to obtain a crude product of the adhesion promoter, wherein the mass ratio of the hydroxypropyl acrylate to the isocyanate groups is 1:1.8-2.2, and the addition amount of the catalyst is 0.1-2wt.% of the total reactant.
3. The method for producing an adhesion promoter for optical fiber coating according to claim 2, further comprising a step of refining the crude product obtained in step (2) by subjecting the crude product to distillation under reduced pressure at 60 to 70 ℃.
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| CN102167925A (en) * | 2011-03-02 | 2011-08-31 | 中国科学院长春应用化学研究所 | Adhesion promoter of optical fiber coating and preparation method thereof |
| CN106188120A (en) * | 2016-07-16 | 2016-12-07 | 北京化工大学 | A kind of bifunctionality acrylate monomer of silicone-containing structure and preparation method thereof |
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