CN117285690A - Flexible optical buffer material and preparation method and application thereof - Google Patents
Flexible optical buffer material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117285690A CN117285690A CN202311191868.XA CN202311191868A CN117285690A CN 117285690 A CN117285690 A CN 117285690A CN 202311191868 A CN202311191868 A CN 202311191868A CN 117285690 A CN117285690 A CN 117285690A
- Authority
- CN
- China
- Prior art keywords
- flexible optical
- polyborosiloxane
- buffer material
- optical buffer
- raw materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- -1 alkoxy silane Chemical compound 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 229920002635 polyurethane Polymers 0.000 claims abstract description 31
- 239000004814 polyurethane Substances 0.000 claims abstract description 31
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000002861 polymer material Substances 0.000 claims abstract description 11
- 229910000077 silane Inorganic materials 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006482 condensation reaction Methods 0.000 claims abstract description 4
- 239000004005 microsphere Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 12
- 239000005056 polyisocyanate Substances 0.000 claims description 11
- 229920001228 polyisocyanate Polymers 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- MEAIMCCQSLMUBK-UHFFFAOYSA-N 3-chloropropyl(ethoxy)silane Chemical compound CCO[SiH2]CCCCl MEAIMCCQSLMUBK-UHFFFAOYSA-N 0.000 claims description 3
- ZLAOXGYWRBSWOY-UHFFFAOYSA-N 3-chloropropyl(methoxy)silane Chemical compound CO[SiH2]CCCCl ZLAOXGYWRBSWOY-UHFFFAOYSA-N 0.000 claims description 3
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical compound CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 claims description 3
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims description 3
- RKKOMEIYHHASIN-UHFFFAOYSA-N hydroperoxyboronic acid Chemical compound OOB(O)O RKKOMEIYHHASIN-UHFFFAOYSA-N 0.000 claims description 3
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims description 3
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000035939 shock Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 40
- 230000001681 protective effect Effects 0.000 description 29
- 239000002313 adhesive film Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 239000002216 antistatic agent Substances 0.000 description 9
- 238000011049 filling Methods 0.000 description 9
- 239000007863 gel particle Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 description 8
- 238000005266 casting Methods 0.000 description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007734 materials engineering Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/61—Polysiloxanes
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- 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 flexible optical buffer material and a preparation method and application thereof, wherein the preparation method comprises the following steps: taking alkoxy silane and halogenated alkyl alkoxy silane as reaction raw materials, and obtaining the linear polysiloxane with silicon hydroxyl end capped and side chain containing halogenated alkyl through hydrolytic condensation reaction; boric acid compounds and silicon hydroxyl end-capped polysiloxane are used as raw materials, and the polyborosiloxane is prepared by heating reaction, washing and drying; hydrolyzing the prepared polyborosiloxane under alkaline conditions to obtain polyborosiloxane with end capped silicon hydroxyl and side chain containing alkyl hydroxyl; mixing a certain amount of polyborosiloxane, polyurethane prepolymer, catalyst and anhydrous solvent, reacting for a certain time at a certain temperature, adding a cross-linking agent, continuing to react for a certain time, and drying to obtain the polyborosiloxane polyurethane polymer material serving as the flexible optical buffer material. The flexible optical buffer material has excellent optical performance, flexibility and shock resistance.
Description
Technical Field
The invention relates to the technical field of optical materials, in particular to a flexible optical buffer material and a preparation method and application thereof.
Background
With the rapid development of communication technology and internet technology and the pursuit of practicality and color of display devices, the development of display devices has been promoted toward multifunction and digitalization. In particular, modern display devices are evolving towards high density, high resolution, energy saving, high brightness, colorization, large screen, flexible, transparent displays, etc. Typically, an optical-grade protective film is provided on the surface of the display to protect the display from external impacts, such as PET, PMMA, PC, TPU, PI, PVC. The optical protective film needs to meet performance requirements of high light transmittance, low haze, high brightness, and the like. The impact resistance and the flexibility of the existing optical protective film are still poor.
Conventional polyurethane elastomer materials rely on the deformation and resilience of the material for cushioning, with limited cushioning capacity. The shearing thixotropic hardened elastomer material can effectively expand the contact area and dissipate energy by means of a polyurethane network. Shear-hardening non-newtonian fluids are a class of materials that are capable of undergoing chemical bond changes when subjected to impact loads. The shear hardening material has not only excellent flexibility and impact resistance, but also excellent thermal stability and plasticity (weaker flowability). Under natural state or low-speed impact, the shear hardening adhesive is in a loose and soft viscous state and shows excellent flexibility. With the increase of external impact load (or frequency), the shear hardening glue can change phase from viscous state to high elastic state, even glass state, and macroscopic behavior is represented by sharp increase of modulus, so that the shear hardening glue can resist impact deformation better and absorb impact energy. When the impact load is lost, the shear hardening adhesive can not only restore to the original viscous state, but also be re-bonded after being broken, and has excellent self-repairing property. The shear hardening adhesive adopts a polymer material-polyborosiloxane, similar to common plasticine in life, and relies on the retarding effect of the breaking speed of boron-oxygen bonds formed by boron atoms and oxygen atoms on microscopic level, so that the shear hardening adhesive is very soft in a natural state, and when being impacted, the boron-oxygen bonds provide very strong resistance, and the stronger the impact load is, the greater the resistance is. The british engineer Richard in 1999 invented that "soft and hard" D3O materials are impact resistant materials of shear-hardening glue systems, which are soft and elastic in normal state, and once they are impacted or extruded at high speed, the molecular chains lock with each other immediately, and the materials become hard and consume external force. When the external force is removed, the material returns to its original flexible state. Due to its excellent impact resistance and excellent flexibility, D3O has been widely used in the impact protection field, such as products of body armor and protective cases for electronic products.
Although the polyborosiloxane material has excellent cushioning properties, its molecular linear structure is easy to flow, and its shape stability cannot be maintained, so that the polyborosiloxane material can be added to other resin materials to maintain its shape. Although the addition and dispersion of materials can be achieved by physical action, the B-O and Si-O bonds themselves belong to inorganic polymer systems, which are difficult to be compatible with PET, TPU, TAC and acrylic systems and the like in the field of optical films, and the poor compatibility results in the light transmittance and haze of the materials to which the polyborosiloxanes are added being greatly affected. In addition, the inorganic materials are easy to separate out from the blend system, so that the thermal oxidative ageing performance and the dimensional stability are poor, the bonding interface stability of other adhesives is poor, and the bonding difficulty is high. There have been no reports on the use of D3O materials for optical protective films.
The Chinese patent application with publication number of CN115181413A provides a strain rate sensitive impact protection material based on polyborosiloxane modified polyurethane, a preparation method and application thereof, wherein the strain rate sensitive impact protection material based on polyborosiloxane modified polyurethane is prepared by compounding polyurethane and polyborosiloxane through a co-foaming process, and the material can be molded and cured in a short time at normal temperature, can change self modulus according to the speed of impacted, presents strain rate sensitivity, realizes self-adaptive energy absorption, and can be applied to buffer protection under various impact conditions. In the material, polyborosiloxane is well dispersed in a polyurethane foam skeleton in a sea-island form, and the polyurethane and polyborosiloxane composite form material is only suitable for foam protective materials, is applied to the fields of aerospace equipment, military protective equipment, sports protective equipment and the like, and cannot be applied to an optical protective film.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a flexible optical buffer material and a preparation method and application thereof. The flexible optical buffer material has excellent optical performance, flexibility and impact resistance, has the elastic buffer performance of polyurethane, has shearing hardening characteristic to realize rapid dispersion of force, further has more remarkable buffer characteristic, realizes effective combination of polyurethane and polyborosiloxane, and solves the problems of low light transmittance, high haze, poor structural stability and poor adhesion of the material caused by poor compatibility of the polyurethane and the polyborosiloxane.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
a method for preparing a flexible optical buffer material, comprising the steps of:
(1) Preparation of Silicohydroxy-terminated polysiloxanes
Taking alkoxy silane and halogenated alkyl alkoxy silane as reaction raw materials, and obtaining the linear polysiloxane with silicon hydroxyl end capped and side chain containing halogenated alkyl through hydrolytic condensation reaction;
(2) Preparation of polyborosiloxanes
Taking boric acid compounds and the silicon hydroxyl end-capped polysiloxane prepared in the step (1) as raw materials, heating for reaction, washing and drying to prepare the polyborosiloxane;
(3) Hydrolysis reaction
Hydrolyzing the polyborosiloxane prepared in the step (2) under alkaline conditions to prepare polyborosiloxane with end-capped silicon hydroxyl and side chain containing alkyl hydroxyl;
(4) Preparation of polyborosiloxane polyurethane polymer material
Mixing a certain amount of polyborosiloxane, polyurethane prepolymer, catalyst and anhydrous solvent, reacting for a certain time at a certain temperature, adding a cross-linking agent, continuing to react for a certain time, and drying to obtain the polyborosiloxane polyurethane polymer material serving as the flexible optical buffer material.
Further, the alkoxy silane is selected from one of methoxy silane, ethoxy silane, propoxy silane and butoxy silane; the haloalkylalkoxysilane is selected from one of 3-chloropropyl methoxysilane, 3-chloropropyl ethoxysilane, 3-chloromethyl methoxysilane and 3-chloromethyl ethoxysilane.
Further, the boric acid compound is selected from one of hydroxy boric acid, alkyl boric acid and aryl boric acid; in the step (2), the molar ratio of hydroxyl groups in the silicon hydroxyl-terminated polysiloxane to hydroxyl groups in the boric acid compound is (0.5-1): 1.
further, the reaction temperature in the step (2) is 80-140 ℃ and the reaction time is 12-24 h.
Further, the polyurethane prepolymer is an isocyanate-terminated polyurethane prepolymer, and the isocyanate-terminated polyurethane prepolymer is prepared by reacting a polyisocyanate compound and a polyhydroxy compound; the molar ratio of isocyanate groups in the polyisocyanate-based compound to hydroxyl groups in the polyol is (1 to 2.5): 1, the reaction temperature of the polyisocyanate-based compound and the polyol is 50 to 80 ℃. Wherein the polyisocyanate-based compound is at least one selected from isophorone diisocyanate and hexamethylene diisocyanate; the polyhydroxy compound is at least one selected from polyether glycol and polyester glycol.
Further, the cross-linking agent in the step (4) is a polyorganosiloxane cross-linking agent or ethyl orthosilicate, and the catalyst is dibutyl tin dilaurate; the reaction temperature of the step (4) is 80-90 ℃.
Further, the mass ratio of the polyurethane prepolymer to the polyborosiloxane in the step (4) is (70-100): (15-30).
The invention further provides a flexible optical buffer material prepared by the preparation method.
The invention further provides application of the flexible optical buffer material to a flexible optical protection film, and specifically, the flexible optical protection film comprises the following raw materials in parts by weight:
75-90 parts of flexible optical buffer material;
10-20 parts of active gel microspheres;
0-5 parts of auxiliary agent.
Further, the active gel microsphere comprises the following raw materials in parts by weight:
the preparation process of the active gel microsphere comprises the following steps:
1) Vacuum dewatering polytetramethylene ether glycol, adding isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate at 30-50 ℃, and reacting at 55-85 ℃ for 3-5 hours to obtain polyurethane prepolymer;
2) Adding trimethylolpropane to chain-extend the polyurethane prepolymer;
3) Adding atactic polyvinyl alcohol, syndiotactic polyvinyl alcohol and QCS aqueous phase solution, and drying to obtain active gel;
4) Feeding the prepared active gel and inorganic salt into a grinding disc-shaped mechanochemical reactor, and carrying out grinding circulation for a plurality of times to obtain active gel particles which are mutually embedded, uniformly mixed and dispersed; the abrasive disk-shaped mechanochemical reactor is self-developed by the key laboratory (university of Sichuan) in the national high molecular materials engineering,
5) The prepared active gel particles are processed by processing equipment and processing technology of gel microsphere materials disclosed in application number 2021111327820, and the specific process is as follows:
s1: vacuumizing the interior of the mixing barrel, then filling inert gas, and sealing the mixing barrel after filling;
s2: filling the prepared active gel particles into the mixing barrel from the charging port, and stopping injecting the raw materials to be mixed when the raw materials in the mixing barrel overflow the top of the flow dividing ring;
s3: turning on a power supply of the processing equipment, enabling the fan-shaped impeller to rotate at a constant speed in the mixing barrel at normal temperature, and standing for 0.5-1h after raw materials in the mixing barrel are uniformly stirred, thus obtaining the active gel microspheres.
The beneficial effects of the invention are as follows:
the polyborosiloxane polyurethane polymer material used as the flexible optical buffer material is a macromolecular polymer network material with a polyborosiloxane network and a polyurethane network interpenetrating or entangled, wherein polyborosiloxane has end-capped silicon hydroxyl groups and alkyl hydroxyl groups positioned on side chains, wherein the alkyl hydroxyl groups on the side chains have good nucleophilicity, covalent bonds can be generated with isocyanate groups in polyurethane, and the end-capped silicon hydroxyl groups can enable the polyborosiloxane to be condensed and crosslinked to form a polyborosiloxane three-dimensional network under the action of a crosslinking agent; covalent bonds formed by the alkyl hydroxyl groups of the polyborosiloxane and the isocyanate groups of the polyurethane serve as chemical crosslinking points of the polyborosiloxane polymer network and the polyurethane polymer network, so that the polyborosiloxane is effectively introduced into the polyurethane polymer network. In the formed polyborosiloxane polyurethane polymer, the polyborosiloxane polymer network and the polyurethane polymer network are interpenetrating and intertwined, and the polyborosiloxane polymer network and the polyurethane polymer network can be prevented from being separated due to the existence of covalent bond bonding points.
The structure form of the polyborosiloxane polyurethane polymer material not only solves the problems of low material light transmittance, high haze, poor structural stability and poor adhesion caused by poor compatibility of polyurethane and polyborosiloxane, but also ensures that the flexible optical buffer material has excellent optical performance, flexibility and impact resistance, and has the elastic buffer performance of polyurethane and shearing hardening characteristic to realize rapid dispersion of force, thereby further having more remarkable buffer characteristic and impact resistance.
The flexible optical protective film manufactured by the flexible optical buffer material after application is converted into a solid state due to the shearing hardening characteristic after being impacted, the impact force is rapidly dispersed, the impact diameter is increased, the impact area is enlarged, and the buffering and energy absorbing characteristics are greatly improved.
The flexible optical buffer material can meet the requirements of folding screens, protective films of other flexible screens and buffer materials in modules, can exert the low-temperature dynamic bending characteristic of organic silicon, and can exert the high-temperature resistant characteristic of a polyurethane elastic network structure.
In addition, the flexible optical protective film contains the active gel microspheres, the active gel microspheres not only can provide more abundant crosslinking points for a polymer network, but also can provide more remarkable shape memory and shape recovery functions for materials by virtue of more abundant and strong acting forces between gel microsphere molecules and between the gel microspheres and polyurethane molecules.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully by reference to the accompanying drawings, in which it is shown, by way of illustration, only some, but not all embodiments of the invention. 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 invention provides a preparation method of a flexible optical buffer material, which comprises the following steps:
(1) Preparation of Silicohydroxy-terminated polysiloxanes
Taking alkoxy silane and halogenated alkyl alkoxy silane as reaction raw materials, and obtaining the linear polysiloxane with silicon hydroxyl end capped and side chain containing halogenated alkyl through hydrolytic condensation reaction;
wherein the alkoxy silane is at least one selected from methoxy silane, ethoxy silane, propoxy silane and butoxy silane; the haloalkylalkoxysilane is selected from one of 3-chloropropyl methoxysilane, 3-chloropropyl ethoxysilane, 3-chloromethyl methoxysilane and 3-chloromethyl ethoxysilane;
(2) Preparation of polyborosiloxanes
Taking boric acid compounds and the silicon hydroxyl end-capped polysiloxane prepared in the step (1) as raw materials, heating for reaction at the temperature of 80-140 ℃ for 12-48 hours, washing and drying after the reaction to prepare the polyborosiloxane; wherein the boric acid compound is selected from one of hydroxy boric acid, alkyl boric acid and aryl boric acid;
in the step (2), the molar ratio of hydroxyl groups in the silicon hydroxyl-terminated polysiloxane to hydroxyl groups in the boric acid compound is (0.5-1): 1, a step of;
(3) Hydrolysis reaction
Hydrolyzing the polyborosiloxane prepared in the step (2) under alkaline conditions to prepare polyborosiloxane with end-capped silicon hydroxyl and side chain containing alkyl hydroxyl; the molecular structural formula of the polyborosiloxane is exemplified as follows:
wherein m+n=20 to 40, and p=10 to 20;
(4) Preparation of polyborosiloxane polyurethane polymer material
Mixing a certain amount of polyborosiloxane, polyurethane prepolymer, catalyst and anhydrous solvent, reacting for a certain time at a certain temperature, adding a cross-linking agent, continuously reacting for a certain time, and drying to remove the solvent to prepare the polyborosiloxane polyurethane polymer material serving as the flexible optical buffer material.
The polyurethane prepolymer is isocyanate-terminated polyurethane prepolymer, and the isocyanate-terminated polyurethane prepolymer is prepared by reacting a polyisocyanate compound and a polyhydroxy compound; the molar ratio of isocyanate groups in the polyisocyanate-based compound to hydroxyl groups in the polyol is (1 to 2.5): 1, the reaction temperature of the polyisocyanate-based compound and the polyol is 50 to 80 ℃. Wherein the polyisocyanate-based compound is at least one selected from isophorone diisocyanate and hexamethylene diisocyanate; the polyhydroxy compound is at least one selected from polyether glycol and polyester glycol.
The cross-linking agent in the step (4) is a polyorganosiloxane cross-linking agent or tetraethoxysilane, and the catalyst is dibutyl tin dilaurate; the reaction temperature of the step (4) is 80-90 ℃.
The mass ratio of the polyurethane prepolymer to the polyborosiloxane in the step (4) is (70-100): (15-30).
The invention further provides a flexible optical buffer material prepared by the preparation method.
The invention further provides application of the flexible optical buffer material to a flexible optical protection film, and specifically, the flexible optical protection film comprises the following raw materials in parts by weight:
75-90 parts of flexible optical buffer material;
10-20 parts of active gel microspheres;
0-5 parts of auxiliary agent.
Wherein the auxiliary agent is selected from antistatic agent, antibacterial agent, etc.
The active gel microsphere comprises the following raw materials in parts by weight:
the preparation process of the active gel microsphere comprises the following steps:
1) After carrying out vacuum dehydration on polytetramethylene ether glycol, adding isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate at 30-50 ℃, and then reacting for 3-5 hours at 55-85 ℃ to obtain polyurethane prepolymer;
2) Adding trimethylolpropane to chain-extend the polyurethane prepolymer;
3) Adding atactic polyvinyl alcohol, syndiotactic polyvinyl alcohol and QCS aqueous phase solution, and drying to obtain active gel;
4) Feeding the prepared active gel and inorganic salt into a grinding disc-shaped mechanochemical reactor, and carrying out grinding circulation for a plurality of times to obtain active gel particles which are mutually embedded, uniformly mixed and dispersed; the abrasive disk-shaped mechanochemical reactor is self-developed by the key laboratory (university of Sichuan) in the national high molecular materials engineering,
5) The prepared active gel particles are processed by processing equipment and processing technology of gel microsphere materials disclosed in application number 2021111327820, and the specific process is as follows:
s1: vacuumizing the interior of the mixing barrel, then filling inert gas, and sealing the mixing barrel after filling;
s2: filling the prepared active gel particles into the mixing barrel from the charging port, and stopping injecting the raw materials to be mixed when the raw materials in the mixing barrel overflow the top of the flow dividing ring;
s3: turning on a power supply of the processing equipment, enabling the fan-shaped impeller to rotate at a constant speed in the mixing barrel at normal temperature, and standing for 0.5-1h after raw materials in the mixing barrel are uniformly stirred, thus obtaining the active gel microspheres.
The preparation process of the flexible optical protective film comprises the following steps:
(1) According to the formula amount, adding a flexible optical buffer material, active gel microspheres and an auxiliary agent into a mixer, and stirring and mixing for 0.5-1h at 60 ℃ and a rotating speed of 50-100rpm to obtain a mixed raw material;
(2) Placing the mixed raw materials obtained in the step (2) into a single screw extruder, wherein the five-section partition temperature of the extruder is 190 ℃, 205 ℃, 220 ℃, 230 ℃, 240 ℃ respectively, performing high-temperature melting co-extrusion at a rotating speed of 45-50rpm, discharging through a casting film die head, and performing casting molding to obtain a primary adhesive film;
(3) And (3) drawing the primary adhesive film obtained in the step (2) onto a drawing roller, and carrying out biaxial stretching, cooling roller shaping, solidifying, slitting and rolling on the primary adhesive film to obtain the flexible optical protective film.
The invention is further illustrated by the following specific examples.
Example 1
The method for preparing the flexible optical buffer material of embodiment 1 includes the following steps:
(1) Preparation of Silicohydroxy-terminated polysiloxanes
In a single-mouth bottle with a magnetic stirring and condensing tube, the molar ratio of the added materials is 1:1, adding a certain amount of deionized water, adding a certain amount of absolute ethyl alcohol for solubilization, taking oxalic acid as a catalyst, adjusting the pH value to 3-4, stirring and reacting for 1-2 h at 30-50 ℃, removing the ethyl alcohol in the system by rotary evaporation, adding distilled water for washing to be neutral, discharging the water at the lower layer, drying by using anhydrous sodium sulfate, and filtering to obtain the polysiloxane with the side chain containing chloropropyl blocked by the silicon hydroxyl group.
(2) Preparation of polyborosiloxanes
Placing phenylboronic acid and the silicon hydroxyl-terminated chloropropyl polysiloxane prepared in the step (1) (the molar ratio of hydroxyl in the silicon hydroxyl-terminated chloropropyl polysiloxane to hydroxyl in the phenylboronic acid is 1:1) into a three-neck round bottom flask provided with a reflux condenser, a nitrogen port and a mechanical stirrer, and heating and reacting for a period of time at 100 ℃; the product was dissolved in dry n-hexane to form a solution, then an appropriate amount of distilled water was added, and unreacted phenylboronic acid was washed out, and this was repeated three times, and finally it was further dried under vacuum at 150 ℃ for 3 hours to obtain a polyborosiloxane having a silicon hydroxyl group-terminated and a chloropropyl group-containing side chain.
(3) Hydrolysis reaction
Adding the polyborosiloxane prepared in the step (2), naOH and water into a reaction vessel, connecting a stirring pipe and a condensing pipe to the reaction vessel, reacting for a certain time at room temperature, extracting by using normal hexane after the reaction is finished, drying an upper organic layer by using anhydrous sodium sulfate, rectifying, collecting the polyborosiloxane of which the target product is silicon hydroxyl-terminated and the side chain contains hydroxypropyl, and filtering a lower hydrolysate for recycling.
(4) Preparation of polyborosiloxane polyurethane polymer material
Mixing the polyurethane prepolymer, the polyborosiloxane prepared in the step (3), dibutyl tin dilaurate and chloroform, reacting for 2 hours at 80 ℃, adding ethyl orthosilicate, continuously reacting for a certain time, and drying to remove the solvent to prepare the polyborosiloxane polyurethane polymer material serving as the flexible optical buffer material; the mass ratio of the polyurethane prepolymer to the polyborosiloxane is 80:20. the mass ratio of the polyborosiloxane to the ethyl orthosilicate to the dibutyl tin dilaurate is 40:3:1, the mass of the chloroform is 3 times of that of the polyborosiloxane.
The polyurethane prepolymer is isocyanate-terminated polyurethane prepolymer, and the isocyanate-terminated polyurethane prepolymer is prepared by reacting isophorone diisocyanate and polyester diol; the molar ratio of isocyanate groups in the isophorone diisocyanate to hydroxyl groups in the polyester diol is 2:1, the reaction temperature of the reaction of the isophorone diisocyanate and the polyester diol is 60 ℃.
Example 2
The difference from example 1 is that: in step (4) of example 2, the mass ratio of polyurethane prepolymer to polyborosiloxane was 70:30.
example 3
The difference from example 1 is that: in step (4) of example 3, the mass ratio of polyurethane prepolymer to polyborosiloxane was 75:25.
example 4
The flexible optical protective film of example 4 is prepared from the following raw materials in parts by weight:
75 parts of the flexible optical buffer material obtained in example 1;
15 parts of active gel microspheres;
1 part of antistatic agent.
The active gel microsphere comprises the following raw materials in parts by weight:
the preparation process of the active gel microsphere comprises the following steps:
1) After carrying out vacuum dehydration on polytetramethylene ether glycol, adding isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate at 35 ℃, and reacting for 3 hours at 65 ℃ to obtain a polyurethane prepolymer;
2) Adding trimethylolpropane to chain-extend the polyurethane prepolymer;
3) Adding atactic polyvinyl alcohol, syndiotactic polyvinyl alcohol and QCS aqueous phase solution, and drying to obtain active gel;
4) Feeding the prepared active gel and inorganic salt into a grinding disc-shaped mechanochemical reactor, and carrying out grinding circulation for a plurality of times to obtain active gel particles which are mutually embedded, uniformly mixed and dispersed;
5) The prepared active gel particles are processed by processing equipment and processing technology of gel microsphere materials disclosed in application number 2021111327820, and the specific process is as follows:
s1: vacuumizing the interior of the mixing barrel, then filling inert gas, and sealing the mixing barrel after filling;
s2: filling the prepared active gel particles into the mixing barrel from the charging port, and stopping injecting the raw materials to be mixed when the raw materials in the mixing barrel overflow the top of the flow dividing ring;
s3: turning on a power supply of the processing equipment, enabling the fan-shaped impeller to rotate at a constant speed in the mixing barrel at normal temperature, and standing for 1h after raw materials in the mixing barrel are uniformly stirred, thus obtaining the active gel microspheres.
The preparation process of the flexible optical protective film comprises the following steps:
(1) According to the formula amount, adding a flexible optical buffer material, active gel microspheres and an antistatic agent into a mixer, and stirring and mixing for 1h at 60 ℃ and a rotating speed of 50-100rpm to obtain a mixed raw material;
(2) Placing the mixed raw materials obtained in the step (2) into a single screw extruder, wherein the five-section partition temperature of the extruder is 190 ℃, 205 ℃, 220 ℃, 230 ℃, 240 ℃ respectively, performing high-temperature melting co-extrusion at a rotating speed of 45-50rpm, discharging through a casting film die head, and performing casting molding to obtain a primary adhesive film;
(3) And (3) drawing the primary adhesive film obtained in the step (2) onto a drawing roller, and carrying out biaxial stretching, cooling roller shaping, solidifying, slitting and rolling on the primary adhesive film to obtain the flexible optical protective film.
Example 5
This embodiment 5 differs from embodiment 4 in that: the flexible optical buffer material was the flexible optical buffer material obtained in example 2.
Example 6
The flexible optical protective film of example 6 is prepared from the following raw materials in parts by weight:
80 parts of the flexible optical buffer material obtained in example 2;
10 parts of active gel microspheres;
1 part of antistatic agent.
Wherein, the preparation method and the formulation of the active gel microsphere and the preparation method of the flexible optical protection film are the same as those of the example 4.
Example 7
The flexible optical protective film of example 7 is prepared from the following raw materials in parts by weight:
90 parts of the flexible optical buffer material obtained in example 3;
20 parts of active gel microspheres;
1 part of antistatic agent.
Wherein, the preparation method and the formulation of the active gel microsphere and the preparation method of the flexible optical protection film are the same as those of the example 4.
Comparative example 1
The optical protective film of the comparative example 1 is prepared from the following raw materials in parts by weight:
75 parts of TPU resin;
15 parts of active gel microspheres;
1 part of antistatic agent.
Wherein, the preparation method and the formulation of the active gel microsphere are the same as those of the example 4.
The optical protective film of comparative example 1 was prepared by:
(1) Adding TPU resin, active gel microspheres and antistatic agent into a mixer according to the formula amount, and stirring and mixing for 1h at 60 ℃ and a rotating speed of 50-100rpm to obtain a mixed raw material;
(2) Placing the mixed raw materials obtained in the step (2) into a single screw extruder, wherein the five-section partition temperature of the extruder is 190 ℃, 205 ℃, 220 ℃, 230 ℃, 240 ℃ respectively, performing high-temperature melting co-extrusion at a rotating speed of 45-50rpm, discharging through a casting film die head, and performing casting molding to obtain a primary adhesive film;
(3) And (3) drawing the primary adhesive film obtained in the step (2) onto a drawing roller, and carrying out biaxial stretching, cooling roller shaping, solidifying, slitting and rolling on the primary adhesive film to obtain the optical protective film.
Comparative example 2
The optical protective film of the comparative example 2 is prepared from the following raw materials in parts by weight:
90 parts of TPU resin;
1 part of antistatic agent.
The optical protective film of comparative example 2 was prepared by:
(1) Adding TPU resin and antistatic agent into a mixer according to the formula amount, stirring and mixing for 1h at 60 ℃ and a rotating speed of 50-100rpm to obtain mixed raw materials;
(2) Placing the mixed raw materials obtained in the step (2) into a single screw extruder, wherein the five-section partition temperature of the extruder is 190 ℃, 205 ℃, 220 ℃, 230 ℃, 240 ℃ respectively, performing high-temperature melting co-extrusion at a rotating speed of 45-50rpm, discharging through a casting film die head, and performing casting molding to obtain a primary adhesive film;
(3) And (3) drawing the primary adhesive film obtained in the step (2) onto a drawing roller, and carrying out biaxial stretching, cooling roller shaping, solidifying, slitting and rolling on the primary adhesive film to obtain the optical protective film.
Performance testing
The optical protective films obtained in examples 4 to 7 of the present invention and comparative examples 1 and 2 were subjected to respective performance tests, and the test results are shown in table 1.
The test method comprises the following steps:
(1) Appearance: the hand-held strong light lamp forms 45 degrees with the film surface, the number and the size of crystal points are observed, and no crystal point or phi is less than or equal to 0.1mm and is recorded as 4; phi is more than 0.1 and less than or equal to 0.2mm crystal point and less than 3/m 2 And is denoted as "3"; phi is more than 0.2 and less than or equal to 0.3mm crystal point and less than 3/m 2 And is marked as '2'; phi > 0.3mm, and is marked as '1'.
(2) Transmittance, haze: the test was conducted according to the method described in JIS K7361.
(3) Ball falling impact: placing the optical protective film on a plane horizontally at 23.5 ℃, enabling 110g of steel balls to fall freely from 130cm, and placing the optical protective film under a microscope to observe the appearance of the film surface, wherein no obvious mark is marked as '4'; slight dents, noted "3"; has obvious dent, which is marked as '2'; obvious marks such as cracks, stress whitening or breakage are marked as '1'.
(4) Impact buffering test: the optical protection film is placed on a force sensor of a falling ball impact tester, a 32g solid steel ball falls down by 50cm, the force sensor detects impact force, and the smaller the impact force peak value is, the better the buffering performance of the material is. The peak impact force in the blank case was 5264N.
(5) Self-repairing efficiency: the film surface is subjected to back and forth operation by using a copper brush at the temperature of 23.5 ℃ under the force of 1kg, stopping after 10 back and forth steps, and observing the repair condition of the film surface, and marking the repair condition as '5' in second repair or 10 s; self-repair within 60s, noted "4"; self-repairing within 120s, which is marked as '3'; self-repairing within 10min, and marking as '2'; over 10min or scratch, recorded as "1".
TABLE 1
As can be seen from Table 1, the optical protective films of examples 4 to 7 of the present invention are capable of effectively reducing impact force, have good cushioning properties, and have excellent optical transmittance, self-repairing properties and low haze.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all modifications or equivalent arrangements using the teachings of this invention, or direct or indirect application in other related arts, are included within the scope of this invention.
Claims (10)
1. A method for preparing a flexible optical buffer material, comprising the steps of:
(1) Preparation of Silicohydroxy-terminated polysiloxanes
Taking alkoxy silane and halogenated alkyl alkoxy silane as reaction raw materials, and obtaining the linear polysiloxane with silicon hydroxyl end capped and side chain containing halogenated alkyl through hydrolytic condensation reaction;
(2) Preparation of polyborosiloxanes
Taking boric acid compounds and the silicon hydroxyl end-capped polysiloxane prepared in the step (1) as raw materials, heating for reaction, washing and drying to prepare the polyborosiloxane;
(3) Hydrolysis reaction
Hydrolyzing the polyborosiloxane prepared in the step (2) under alkaline conditions to prepare polyborosiloxane with end-capped silicon hydroxyl and side chain containing alkyl hydroxyl;
(4) Preparation of polyborosiloxane polyurethane polymer material
Mixing a certain amount of polyborosiloxane, polyurethane prepolymer, catalyst and anhydrous solvent, reacting for a certain time at a certain temperature, adding a cross-linking agent, continuing to react for a certain time, and drying to obtain the polyborosiloxane polyurethane polymer material serving as the flexible optical buffer material.
2. The method for preparing a flexible optical buffer material according to claim 1, wherein: the alkoxy silane is selected from one of methoxy silane, ethoxy silane, propoxy silane and butoxy silane; the haloalkylalkoxysilane is selected from one of 3-chloropropyl methoxysilane, 3-chloropropyl ethoxysilane, 3-chloromethyl methoxysilane and 3-chloromethyl ethoxysilane.
3. The method for preparing a flexible optical buffer material according to claim 1, wherein: the boric acid compound is selected from one of hydroxy boric acid, alkyl boric acid and aryl boric acid; in the step (2), the molar ratio of hydroxyl groups in the silicon hydroxyl-terminated polysiloxane to hydroxyl groups in the boric acid compound is (0.5-1): 1.
4. the method for preparing a flexible optical buffer material according to claim 1, wherein: the reaction temperature in the step (2) is 80-140 ℃ and the reaction time is 12-48 h.
5. The method for preparing a flexible optical buffer material according to claim 1, wherein: the polyurethane prepolymer is isocyanate-terminated polyurethane prepolymer, and the isocyanate-terminated polyurethane prepolymer is prepared by reacting a polyisocyanate compound and a polyhydroxy compound; the molar ratio of isocyanate groups in the polyisocyanate-based compound to hydroxyl groups in the polyol is (1 to 2.5): 1, the reaction temperature of the polyisocyanate-based compound and the polyol is 50 to 80 ℃.
6. The method for preparing a flexible optical buffer material according to claim 1, wherein: the cross-linking agent in the step (4) is a polyorganosiloxane cross-linking agent or tetraethoxysilane, and the catalyst is dibutyl tin dilaurate; the reaction temperature of the step (4) is 80-90 ℃.
7. The method for preparing a flexible optical buffer material according to claim 1, wherein: the mass ratio of the polyurethane prepolymer to the polyborosiloxane in the step (4) is (70-100): (15-30).
8. A flexible optical buffer material produced by the production method of any one of claims 1 to 7.
9. The application of the flexible optical buffer material in the flexible optical protection film as claimed in claim 8, wherein the flexible optical protection film comprises the following raw materials in parts by weight:
75-90 parts of flexible optical buffer material;
10-20 parts of active gel microspheres;
0-5 parts of auxiliary agent.
10. The application of the flexible optical buffer material on the flexible optical protection film according to claim 9, wherein the active gel microsphere comprises the following raw materials in parts by weight:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311191868.XA CN117285690B (en) | 2023-09-15 | Flexible optical buffer material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311191868.XA CN117285690B (en) | 2023-09-15 | Flexible optical buffer material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117285690A true CN117285690A (en) | 2023-12-26 |
| CN117285690B CN117285690B (en) | 2024-05-10 |
Family
ID=
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839443A (en) * | 1987-02-04 | 1989-06-13 | Chisso Corporation | Polysiloxane containing hydroxyl groups and a silicone-modified polyurethane using the same |
| US20110021736A1 (en) * | 2008-03-04 | 2011-01-27 | Bizhong Zhu | Polyborosiloxane and Method of Preparing Same |
| CN105670259A (en) * | 2014-11-21 | 2016-06-15 | 合肥杰事杰新材料股份有限公司 | Polyborosiloxane flame retardant, polycarbonate composite material containing the same, and preparation method thereof |
| CN110564164A (en) * | 2019-09-27 | 2019-12-13 | 中国科学院长春应用化学研究所 | Waterproof polyborosiloxane shock-resistant damping material and preparation method thereof |
| CN111285994A (en) * | 2020-03-23 | 2020-06-16 | 深圳倍达飞科技有限公司 | High-damping wide-damping temperature range shock absorption and energy absorption modifier and preparation method thereof |
| CN112004862A (en) * | 2018-04-25 | 2020-11-27 | 汉高股份有限及两合公司 | Process for preparing hydroxy-functionalized polyether-polysiloxane block copolymers |
| CN112679690A (en) * | 2020-12-25 | 2021-04-20 | 深圳中科先进材料有限公司 | Energy-absorbing material and preparation method thereof |
| CN112940211A (en) * | 2021-04-01 | 2021-06-11 | 深圳市安品有机硅材料有限公司 | Hydroxyl silicone oil modified polyurethane resin, coating and preparation method thereof |
| CN113105605A (en) * | 2021-04-06 | 2021-07-13 | 杭州师范大学 | UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material and preparation and application thereof |
| CN114958171A (en) * | 2022-06-08 | 2022-08-30 | 刘小群 | Preparation method of polyborosiloxane modified polyurethane water-based paint |
| CN115181413A (en) * | 2022-06-30 | 2022-10-14 | 华南理工大学 | Strain rate sensitive impact protection material based on polyborosiloxane modified polyurethane and preparation method and application thereof |
| CN115710425A (en) * | 2022-11-10 | 2023-02-24 | 云南迈特力医疗技术有限公司 | Energy-absorbing material and preparation method thereof |
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839443A (en) * | 1987-02-04 | 1989-06-13 | Chisso Corporation | Polysiloxane containing hydroxyl groups and a silicone-modified polyurethane using the same |
| US20110021736A1 (en) * | 2008-03-04 | 2011-01-27 | Bizhong Zhu | Polyborosiloxane and Method of Preparing Same |
| CN105670259A (en) * | 2014-11-21 | 2016-06-15 | 合肥杰事杰新材料股份有限公司 | Polyborosiloxane flame retardant, polycarbonate composite material containing the same, and preparation method thereof |
| CN112004862A (en) * | 2018-04-25 | 2020-11-27 | 汉高股份有限及两合公司 | Process for preparing hydroxy-functionalized polyether-polysiloxane block copolymers |
| CN110564164A (en) * | 2019-09-27 | 2019-12-13 | 中国科学院长春应用化学研究所 | Waterproof polyborosiloxane shock-resistant damping material and preparation method thereof |
| CN111285994A (en) * | 2020-03-23 | 2020-06-16 | 深圳倍达飞科技有限公司 | High-damping wide-damping temperature range shock absorption and energy absorption modifier and preparation method thereof |
| CN112679690A (en) * | 2020-12-25 | 2021-04-20 | 深圳中科先进材料有限公司 | Energy-absorbing material and preparation method thereof |
| CN112940211A (en) * | 2021-04-01 | 2021-06-11 | 深圳市安品有机硅材料有限公司 | Hydroxyl silicone oil modified polyurethane resin, coating and preparation method thereof |
| CN113105605A (en) * | 2021-04-06 | 2021-07-13 | 杭州师范大学 | UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material and preparation and application thereof |
| CN114958171A (en) * | 2022-06-08 | 2022-08-30 | 刘小群 | Preparation method of polyborosiloxane modified polyurethane water-based paint |
| CN115181413A (en) * | 2022-06-30 | 2022-10-14 | 华南理工大学 | Strain rate sensitive impact protection material based on polyborosiloxane modified polyurethane and preparation method and application thereof |
| CN115710425A (en) * | 2022-11-10 | 2023-02-24 | 云南迈特力医疗技术有限公司 | Energy-absorbing material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| ZHAO, XW (ZHAO, XIONGWEI) [1] ; ZANG, CG (ZANG, CHONGGUANG) [1] ; SUN, YL (SUN, YALUN) [1] ; LIU, KG (LIU, KAIGUO) [1] ; WEN, YQ (: "Borosiloxane oligomers for improving adhesion of addition-curable liquid silicone rubber with epoxy resin by surface treatment", JOURNAL OF MATERIALS SCIENCE, vol. 53, no. 2, 28 December 2018 (2018-12-28), pages 1167 - 1177, XP036349302, DOI: 10.1007/s10853-017-1589-1 * |
| 卢仁杰;韩冰;李锦春;: "GF增强PLA复合材料的界面设计及性能研究", 工程塑料应用, no. 04, 30 April 2010 (2010-04-30), pages 25 - 29 * |
| 晏义伍;范震;曹海琳;: "高抗冲击聚硼硅氧烷微凝胶的合成和性能表征", 中国个体防护装备, no. 06, 15 December 2016 (2016-12-15), pages 5 - 8 * |
| 袁芳;王胜;桑敏;刘梅;白林凤;江万权;龚兴龙;: "磁性剪切增稠复合材料的制备及其磁力耦合特性研究", 中国科学:物理学 力学 天文学, no. 09, 1 September 2018 (2018-09-01), pages 205 - 214 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11926757B2 (en) | Quick-drying solvent-free sag-resistant polyurethane waterproof coating and preparation method therefor | |
| CN1188442C (en) | Impact resistant polyurethane and method of manufacture thereof | |
| CN104774569A (en) | Antistatic surface protection film | |
| CN101033287A (en) | High solid content water polyurethane adhesive for non-absorbability base material and preparing method | |
| CN108503783B (en) | Thermoplastic polyurethane elastomer and preparation method thereof | |
| CN110218290B (en) | Synthetic method of tough, transparent, fluorescent and antibacterial polyurethane film | |
| CN109912771B (en) | Low-precipitation long-acting yellowing-resistant thermoplastic polyurethane elastomer and preparation method thereof | |
| CN110591533B (en) | Environment-friendly laminating coating composition and preparation method thereof | |
| CN113980193B (en) | Optical-grade oleophilic type thermal repair resin, preparation method thereof and self-repair coating | |
| CN108949090B (en) | Solvent-free two-component polyurethane sealant and preparation method thereof | |
| CN111978912A (en) | Organic silicon modified polyurethane sealing material and preparation method thereof | |
| CN110982027A (en) | Polyurethane composition for CL-20 explosive cladding and preparation method thereof | |
| CN117285690B (en) | Flexible optical buffer material and preparation method and application thereof | |
| CN101568579B (en) | Plasticizer for resin and resin composition containing the same | |
| CN113637208B (en) | PET recycling environment-friendly release film | |
| Xu et al. | Tough self-healing polyurethane elastomers based on interpenetrating networks containing multiple hydrogen bond networks, flexible blocks, metal coordination and covalent cross-linking | |
| JP6262999B2 (en) | Shock absorbing film | |
| CN117285690A (en) | Flexible optical buffer material and preparation method and application thereof | |
| CN1113073C (en) | Polyurethanes and polyester polyols | |
| CN106674480B (en) | Preparation method of NDI (Newcastle disease) -modified MDI (diphenylmethane diisocyanate) -based polyurethane microporous elastomer | |
| CN115232593B (en) | Cold and hot shock resistant flame retardant type bi-component polyurethane structural adhesive and preparation method thereof | |
| CN112079987A (en) | Body flame-retardant thermoplastic polyurethane elastomer and preparation method thereof | |
| CN101831047A (en) | Synthesis method of high-performance thermoplastic polyurethane elastomer | |
| Ding et al. | Thermally reversible, self-healing polyurethane based on propyl gallate and polyurethane prepolymers with varied isocyanate content | |
| CN116355384A (en) | Buffering and energy-absorbing GPU film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |