CN115160525A - Polyurethane resin and preparation method and application thereof - Google Patents
Polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN115160525A CN115160525A CN202210426564.6A CN202210426564A CN115160525A CN 115160525 A CN115160525 A CN 115160525A CN 202210426564 A CN202210426564 A CN 202210426564A CN 115160525 A CN115160525 A CN 115160525A
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- polyurethane resin
- polyurethane
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- adhesive
- catalyst
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 23
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 16
- 229920000570 polyether Polymers 0.000 claims abstract description 16
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 11
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920002635 polyurethane Polymers 0.000 claims description 42
- 239000004814 polyurethane Substances 0.000 claims description 42
- 239000000853 adhesive Substances 0.000 claims description 31
- 230000001070 adhesive effect Effects 0.000 claims description 31
- 230000001681 protective effect Effects 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 239000002216 antistatic agent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- -1 isocyanic acid radical Chemical class 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- ALFHRKFVQOIIAA-UHFFFAOYSA-N N=C=O.N=C=O.OCCOCCOCCO Chemical compound N=C=O.N=C=O.OCCOCCOCCO ALFHRKFVQOIIAA-UHFFFAOYSA-N 0.000 description 5
- 229920013701 VORANOL™ Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 206010024769 Local reaction Diseases 0.000 description 2
- 229920001222 biopolymer Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AENCGFOMQCMUBM-UHFFFAOYSA-K ethyltin(3+) hexanoate Chemical compound CC[Sn+3].CCCCCC([O-])=O.CCCCCC([O-])=O.CCCCCC([O-])=O AENCGFOMQCMUBM-UHFFFAOYSA-K 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
-
- 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
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/08—Polyurethanes from polyethers
Abstract
The invention discloses a polyurethane resin and a preparation method and application thereof, and the preparation raw materials of the polyurethane resin comprise: polyether polyol, hexamethylene diisocyanate and a catalyst; the catalyst is dibutyltin dilaurate and tin 2-ethyl hexanoate; in the polyurethane resin, the molar ratio of hydroxyl to isocyanic acid radical is 1.07-1.21: 1; the solid content of the polyurethane resin is 55-75%; the molecular weight of the polyether polyol is 1000-2000; the viscosity of the polyurethane resin at 25 ℃ is 4000-12000mpa.s, the macromolecular polyurethane resin is formed by polyether polyol and hexamethylene diisocyanate under the action of a catalyst, the polyurethane resin has the characteristic of low impurity, and meanwhile, the stable hydroxyl content can be provided, so that the polyurethane resin is ensured not to gel.
Description
Technical Field
The invention belongs to the technical field of flexible circuit boards, and particularly relates to polyurethane resin and a preparation method and application thereof.
Background
The polyurethane adhesive refers to an adhesive containing a urethane group or an isocyanate group in a molecular chain. The adhesive film has the characteristics of good flexibility, impact resistance, flexibility, very good ultralow temperature resistance, oil resistance, wear resistance and the like, and is used as an environment-friendly adhesive and enters various fields of industry, agriculture, traffic, medicine, national defense and daily life.
In the smart phone processing industry chain, after ITO glass (ITO conductive glass is based on soda-lime-based or silicon-boron-based substrate glass, a layer of indium tin oxide is plated by a magnetron sputtering method), OGS glass (OGS is an electronic product protection screen manufactured under the technology of directly forming an ITO conductive film and a sensor on protection glass) and cover plate glass are cut, a protection film needs to be attached to prevent the glass from being damaged or polluted in the transportation process, a PET base film has high strength and is easy to punch into various shapes, and the area needing to be protected can be accurately positioned through a positioning hole, so that the protection method is very suitable for protecting the processed conductive glass. However, the existing polyurethane protective film has the problem of low cleanliness of polyurethane resin in the raw materials for preparing the polyurethane protective film, so that the requirements of a smart phone on high light transmittance and low film tearing voltage of the protective film are difficult to meet.
In summary, a polyurethane resin is provided, so that a polyurethane adhesive and a polyurethane protective film prepared from the polyurethane resin as a raw material can provide a stable hydroxyl content, and can achieve the effects of high light transmittance, low haze and low impurities.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. The polyurethane resin provided by the invention is formed by polyether polyol and hexamethylene diisocyanate under the action of a catalyst, so that the stable hydroxyl content can be provided, and the polyurethane resin is ensured not to have a gel phenomenon, so that the prepared polyurethane adhesive has the performances of ultralow peeling force and high light transmittance.
The invention also provides a preparation method of the polyurethane resin.
The invention also provides a polyurethane adhesive, and the raw materials for preparing the adhesive comprise the polyurethane resin.
The invention also provides a polyurethane protective film, and the raw materials for preparing the polyurethane protective film comprise the adhesive.
The first aspect of the present invention provides a polyurethane resin, which is prepared from the following raw materials: polyether polyol, hexamethylene diisocyanate and a catalyst;
the catalyst is dibutyltin dilaurate and tin 2-ethyl hexanoate;
in the polyurethane resin, the molar ratio of hydroxyl to isocyanic acid radical is 1.07-1.21: 1;
the solid content of the polyurethane resin is 55-75%;
the molecular weight of the polyether polyol is 1000-2000;
the viscosity of the polyurethane resin at 25 ℃ is 4000-12000mpa.s.
The polyether polyol and hexamethylene diisocyanate selected in the invention are main reaction bodies, the molecular weight can be rapidly increased under the condition of a catalyst, micromolecular polyether polyol is changed into macromolecular polyurethane resin with low impurity content, and stable hydroxyl content can be provided, which is the key for ensuring that the polyurethane resin is not gelled.
In some embodiments of the invention, the polyether polyol comprises one of VORANOL 1000LM, VORANOL 2120, and VORANOL 2000 LM.
When the molecular weight of the selected polyether polyol resin is low, the adhesive prepared by taking the resin as a raw material is easy to remain adhesive after being attached to the surface of glass.
In some embodiments of the present invention, the raw materials for preparing the polyurethane resin further include: a solvent;
the solvent includes at least one of toluene, xylene, and cyclohexanone.
In some embodiments of the invention, the mass ratio of the dibutyltin dilaurate to the tin 2-ethylhexanoate in the catalyst is from 1 to 25:1.
when dibutyltin dilaurate is used alone, the reaction speed is too high, so that the heating speed is increased; meanwhile, in the reaction process, the local reaction speed is too high, the formed polyurethane resin with the ultrahigh molecular weight is agglomerated into solid, so that a microcapsule is generated, the unreacted hexamethylene diisocyanate is wrapped by the microcapsule, the reaction is incomplete, if the formed polyurethane resin with the ultrahigh molecular weight is too much, plastic is formed, the polyurethane resin does not have the adhesive capability, the temperature rise rate of the system is obviously reduced when the dibutyltin dilaurate and the tin 2-ethylhexanoate are used in a matched manner, and the stability of the obtained main resin among viscosity batches is obviously improved.
In some embodiments of the present invention, the polyurethane resin is prepared from the following raw materials in parts by weight: 55 to 65 portions of polyether polyol, 8 to 12 portions of hexamethylene diisocyanate, 0.01 to 0.3 portion of dibutyltin dilaurate, 0.006 to 0.01 portion of 2-ethyl tin hexanoate and 58.1 to 65 portions of toluene.
The second aspect of the present invention provides a method for preparing the above polyurethane resin, comprising the steps of: mixing the polyurethane resin, hexamethylene diisocyanate, and a catalyst.
In some embodiments of the invention, the mixing time is 0.5 to 2 hours.
In some embodiments of the invention, the temperature of the mixing is between 80 ℃ and 90 ℃.
In some embodiments of the invention, the mixed heating temperature is 40-60 ℃, and the system is heated during the reaction process, so when the temperature is raised to 80-90 ℃, the reaction is kept for 1-2 h.
In some embodiments of the present invention, the method for preparing the polyurethane resin further comprises adjusting the solid content of the resulting system to 55 to 65% after mixing.
The third aspect of the invention provides a polyurethane adhesive, and the preparation raw materials comprise the polyurethane resin.
In some embodiments of the present invention, the raw materials for preparing the polyurethane adhesive further comprise: and (4) an auxiliary agent.
In some embodiments of the invention, the coagent comprises a hexamethylene diisocyanate dipolymer, a plasticizer, an antistatic agent, and an antioxidant.
In some embodiments of the invention, the hexamethylene diisocyanate biopolymer comprises a kesichun N100 resin.
In some embodiments of the invention, the plasticizer comprises triethylene glycol diisocyanate.
The plasticizer has the capability of reducing the system resistance, and can quickly conduct away static electricity generated during film tearing, so that the effect of low film tearing voltage is achieved.
In some embodiments of the invention, the antistatic agent comprises 3M FC4400.
The addition of the ionic antistatic agent of FC4400 ensures that the polyurethane adhesive is low, and the resistance of the whole system is reduced.
In some embodiments of the invention, the antioxidant comprises basf 1010.
In some embodiments of the present invention, the polyurethane adhesive is prepared from the following raw materials in parts by weight: 55-70 parts of polyurethane resin, 5-20 parts of binary polymer of hexamethylene diisocyanate, 10-30 parts of plasticizer, 0.2-1.5 parts of antistatic agent and 0.2-1.0 part of antioxidant.
In some embodiments of the present invention, the method of preparing the polyurethane adhesive comprises: mixing the polyurethane resin, the hexamethylene diisocyanate biopolymer, the plasticizer, the antistatic agent and the antioxidant.
In some embodiments of the invention, the mixing time is 2 to 3 hours.
In some embodiments of the invention, the temperature of the mixing is 40 to 90 ℃.
The fourth aspect of the invention provides a polyurethane protective film, and the preparation raw materials comprise the polyurethane adhesive.
In some embodiments of the present invention, the polyurethane resin mixture is coated on the surface of the PET film and dried to obtain the polyurethane protective film.
In some embodiments of the invention, the coating has a thickness of 8 to 25 μm.
In some embodiments of the invention, the temperature of the drying is 80 to 150 ℃.
In some embodiments of the invention, the drying time is 1 to 8min.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive efforts are within the scope of the present invention.
Example 1
The embodiment prepares a polyurethane resin, which specifically comprises the following components:
s1: dow VORANOL 1000LM 55 parts, dibutyltin dilaurate 0.065 parts, 2-ethyl hexanoate 0.006 part, hexamethylene diisocyanate 9.29 parts and toluene 58.1 parts are put into a four-neck flask to be heated to 60 ℃ to trigger reaction, the system is heated due to reaction heat release, when the temperature is heated to 90 ℃, the temperature is controlled at 90 ℃ to carry out heat preservation reaction for 2 hours,
s2: when the isocyanate group is not reduced any more by using an infrared analyzer, the experiment is immediately stopped, the solid content of the polyurethane resin is adjusted to 65 percent by using toluene, and the polyurethane resin with the viscosity of 1000-15000 cp (which is changed along with the reaction temperature and the stability) is obtained.
Example 2
The embodiment prepares a polyurethane adhesive, which specifically comprises the following steps:
55 parts of the polyurethane resin obtained in example 1, 7.7 parts of N100 resin, 19 parts of triethylene glycol diisocyanate, 0.5 part of 3M FC4400.5 part of BASF 1010.66 part of NBR. And putting the mixture into a four-neck flask, and stirring the mixture for 2 hours at a speed of 300rpm/min to obtain the polyurethane resin adhesive.
Example 3
The embodiment prepares a polyurethane protective film, and specifically comprises the following steps:
the polyurethane resin mixed solution obtained in example 2 was coated on the surface of a PET film to a thickness of 10 μm, and dried in an oven at 120 ℃ for 2min to obtain a polyurethane protective film.
Example 4
The embodiment provides a preparation method of a polyurethane protective film, which specifically comprises the following steps:
the amount of the N100 resin in example 2 was adjusted to 10 parts by mass, and the other conditions were kept unchanged, namely 55 parts of the urethane resin obtained in example 1, 10 parts of the N100 resin, 19 parts of triethylene glycol diisocyanate, 3m fc4400.5 parts, and 0.66 parts of basf 1010. Putting the mixture into a four-neck flask and stirring the mixture for 2 hours at the speed of 300rpm to obtain the polyurethane resin adhesive,
example 5
The embodiment provides a preparation method of a polyurethane protective film, which specifically comprises the following steps:
the antistatic agent in example 2 was adjusted to 1 part by mass, and the other conditions were kept unchanged, namely 55 parts of the polyurethane resin obtained in example 1, 10 parts of N100 resin, 19 parts of triethylene glycol diisocyanate, 3m FC4400 parts, and 0.66 parts of basf 1010. And putting the mixture into a four-neck flask, and stirring the mixture for 2 hours at a speed of 300rpm/min to obtain the polyurethane resin adhesive.
Example 6
The embodiment provides a preparation method of a polyurethane protective film, which specifically comprises the following steps:
this example provides a method for preparing a polyurethane protective film, wherein the antioxidant in example 5 is adjusted to 1 part by mass, and the other conditions are kept unchanged, namely 55 parts of the polyurethane resin obtained in example 1, 10 parts of N100 resin, 19 parts of triethylene glycol diisocyanate, 3m FC4400 parts, and 1010 parts of basf 1010. And putting the mixture into a four-neck flask, and stirring the mixture for 2 hours at a speed of 300rpm/min to obtain the polyurethane resin adhesive.
Comparative example 1
This comparative example provides a method of preparing a polyurethane protective film by replacing the Dow void 1000LM of molecular weight 1000 of example 3 with Dow void 2104 of molecular weight 410, with the rest of the conditions.
Comparative example 2
This comparative example provides a polyurethane protective film, replacing the hexamethylene diisocyanate in example 3 with 4,4' -diphenylmethane diisocyanate, with the same other conditions.
Comparative example 3
This comparative example provides a method for producing a polyurethane protective film, replacing dibutyltin laurate and tin 2-ethylhexanoate in example 3 with tetrabutyl titanate, and the other conditions were the same.
Comparative example 4
This comparative example provides a method for preparing a polyurethane protective film, wherein tin 2-ethylhexanoate in example 3 is absent, and the other conditions are the same.
Test example:
this test example tested the performance of the polyurethane protective films of examples 1 to 4 and comparative examples 1 to 5, and the results are shown in table 1.
TABLE 1 Properties of polyurethane protective films
Examples 3 to 6 form a macromolecular polyurethane resin from polyether polyol and hexamethylene diisocyanate under the action of a catalyst, and the macromolecular polyurethane resin has the characteristic of low impurities, so that a polyurethane adhesive and a polyurethane protective film prepared by continuous reaction have the characteristics of low peeling force and high light transmittance, the polyether polyol in comparative example 1 has a low molecular weight, so that the prepared polyurethane adhesive and polyurethane protective film have a residual glue phenomenon, the side reactions are more after the hexamethylene diisocyanate is replaced by 4,4' -diphenylmethane diisocyanate in comparative example 2, and the resin gel cannot be used, and the titanate catalyst used in comparative example 3 has low catalytic efficiency, and the residual glue and white mist are generated due to more monomer residues. In comparative example 4, only dibutyltin dilaurate is used as a catalyst, and when dibutyltin dilaurate is used alone, the reaction speed is too high, so that the temperature rise speed is increased; meanwhile, during the reaction process, the local reaction speed is too high, which can result in the formation of polyurethane solid with ultra-large molecular weight, thereby resulting in the formation of microcapsule, the microcapsule can wrap unreacted hexamethylene diisocyanate, resulting in incomplete reaction, thereby resulting in incomplete reaction of HDI, and the formation of dimer and even trimer of HDI under the condition of catalyst, and forming a small range of cross-linking. And the residual micromolecular polyether polyol is easy to separate out to cause a white fog phenomenon during environmental test.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The polyurethane resin is characterized by comprising the following preparation raw materials: polyether polyol, hexamethylene diisocyanate and a catalyst;
the catalyst is dibutyltin dilaurate and tin 2-ethyl hexanoate;
in the polyurethane resin, the molar ratio of hydroxyl to isocyanic acid radical is 1.07-1.21: 1;
the solid content of the polyurethane resin is 0.55-0.75;
the molecular weight of the polyether polyol is 1000-2000;
the viscosity of the polyurethane resin at 25 ℃ is 4000-12000mpa.s.
2. The polyurethane resin according to claim 1, wherein the raw materials for preparation further comprise: a solvent, a water-soluble organic solvent,
the solvent comprises one of toluene, xylene and cyclohexanone.
3. The polyurethane resin according to claim 1, wherein the mass ratio of dibutyltin dilaurate to tin 2-ethylhexanoate in the catalyst is from 1 to 25:1.
4. a method for preparing the polyurethane resin according to claim 1, comprising the steps of: the polyurethane resin, hexamethylene diisocyanate and the catalyst are dispersed and mixed.
5. The method for producing a polyurethane resin according to claim 4, wherein the mixing temperature is 80 to 90 ℃.
6. A polyurethane adhesive characterized in that a raw material for production comprises the polyurethane resin as claimed in any one of claims 1 to 5.
7. The polyurethane adhesive of claim 6, wherein the polyurethane adhesive is prepared from the following raw materials: and (4) an auxiliary agent.
8. The polyurethane adhesive of claim 7, wherein the auxiliary agents include a binary polymer of hexamethylene diisocyanate, a plasticizer, an antistatic agent, and an antioxidant.
9. The polyurethane adhesive of claim 8, wherein the polyurethane adhesive is prepared from the following raw materials in parts by weight: 55-70 parts of polyurethane resin, 5-20 parts of binary polymer of hexamethylene diisocyanate, 10-30 parts of plasticizer, 0.2-1.5 parts of antistatic agent and 0.2-1.0 part of antioxidant.
10. A polyurethane protective film characterized in that a preparation raw material comprises the adhesive according to any one of claims 7 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000073040A (en) * | 1998-08-31 | 2000-03-07 | Toyo Ink Mfg Co Ltd | Polyurethane adhesive composition and coated product using the composition |
| JP2000256639A (en) * | 1999-03-08 | 2000-09-19 | Toyo Ink Mfg Co Ltd | Polyurethane adhesive composition and coated material made by using the composition |
| CN104558503A (en) * | 2014-12-25 | 2015-04-29 | 苏州赛伍应用技术有限公司 | Preparation method for polyurethane adhesive applied to protective film |
| CN112251184A (en) * | 2020-10-15 | 2021-01-22 | 苏州赛伍应用技术股份有限公司 | Polyurethane adhesive, PU protective film, preparation method and application thereof |
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2022
- 2022-04-22 CN CN202210426564.6A patent/CN115160525A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000073040A (en) * | 1998-08-31 | 2000-03-07 | Toyo Ink Mfg Co Ltd | Polyurethane adhesive composition and coated product using the composition |
| JP2000256639A (en) * | 1999-03-08 | 2000-09-19 | Toyo Ink Mfg Co Ltd | Polyurethane adhesive composition and coated material made by using the composition |
| CN104558503A (en) * | 2014-12-25 | 2015-04-29 | 苏州赛伍应用技术有限公司 | Preparation method for polyurethane adhesive applied to protective film |
| CN112251184A (en) * | 2020-10-15 | 2021-01-22 | 苏州赛伍应用技术股份有限公司 | Polyurethane adhesive, PU protective film, preparation method and application thereof |
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