CN116874722A - Organosilicon/polyurethane/epoxy resin composite emulsion and preparation method and application thereof - Google Patents
Organosilicon/polyurethane/epoxy resin composite emulsion and preparation method and application thereof Download PDFInfo
- Publication number
- CN116874722A CN116874722A CN202310657361.2A CN202310657361A CN116874722A CN 116874722 A CN116874722 A CN 116874722A CN 202310657361 A CN202310657361 A CN 202310657361A CN 116874722 A CN116874722 A CN 116874722A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- polyurethane
- organosilicon
- glass fiber
- resin composite
- 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.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 113
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 113
- 239000004814 polyurethane Substances 0.000 title claims abstract description 85
- 239000000839 emulsion Substances 0.000 title claims abstract description 80
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000004945 emulsification Methods 0.000 title description 2
- 239000003365 glass fiber Substances 0.000 claims abstract description 115
- 239000000463 material Substances 0.000 claims abstract description 86
- 239000010687 lubricating oil Substances 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004970 Chain extender Substances 0.000 claims abstract description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 21
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 229920002545 silicone oil Polymers 0.000 claims abstract description 17
- 239000000805 composite resin Substances 0.000 claims abstract description 15
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229920001558 organosilicon polymer Polymers 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims description 41
- 239000011347 resin Substances 0.000 claims description 41
- 238000001914 filtration Methods 0.000 claims description 32
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 238000004513 sizing Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- -1 alicyclic isocyanate Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 9
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 238000009775 high-speed stirring Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 46
- 239000003921 oil Substances 0.000 description 28
- 230000014759 maintenance of location Effects 0.000 description 14
- 239000004925 Acrylic resin Substances 0.000 description 13
- 229920000178 Acrylic resin Polymers 0.000 description 13
- 229920001187 thermosetting polymer Polymers 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000012545 processing Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 230000003014 reinforcing effect Effects 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- YPFUJZAAZJXMIP-UHFFFAOYSA-N 3-sulfopropanediol Chemical compound OCC(O)CS(O)(=O)=O YPFUJZAAZJXMIP-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229920013646 Hycar Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 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 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2003—Glass or glassy material
- B01D39/2017—Glass or glassy material the material being filamentary or fibrous
-
- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- 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
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- 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
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- 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
- C08J2375/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Filtering Materials (AREA)
Abstract
The invention provides an organosilicon/polyurethane/epoxy resin composite emulsion, a preparation method and application thereof. The preparation method comprises the following steps: (1) After polyethylene glycol and hydroxyl silicone oil are dehydrated, diisocyanate is added, and the organosilicon/polyurethane prepolymer is prepared by heating reaction; (2) Adding a hydrophilic chain extender to continue the reaction to obtain a hydrophilic organosilicon/polyurethane prepolymer; (3) Adding a diluent and epoxy resin, and reacting to obtain an organosilicon/polyurethane/epoxy resin composite resin system; (4) cooling and adding a neutralizing agent; (5) Adding water under high-speed stirring to form organosilicon/polyurethane/epoxy resin composite emulsion; (6) distilling off the diluent under reduced pressure. The organosilicon/polyurethane/epoxy resin composite emulsion provided by the invention can be applied to the reinforcement of a lubricating oil filter glass fiber filter material after being compounded with a water-based curing agent, and the reinforced filter material can meet the working condition application requirements of a pleating process and 220 ℃ high-temperature resistant lubricating oil.
Description
Technical Field
The invention belongs to the technical field of high polymer materials and filter materials, and particularly relates to an organosilicon/polyurethane/epoxy resin composite emulsion, a preparation method thereof and application of the organosilicon/polyurethane/epoxy resin composite emulsion in a high-temperature-resistant lubricating oil filter material.
Background
The lubricating oil plays roles of reducing friction, reducing abrasion, cooling, preventing corrosion and the like in engine lubricating systems of airplanes, ships and the like, and is known as blood of mechanical equipment. Practice shows that the lubricating oil is easily polluted by solid particles and water molecules, so that the damage such as fatigue wear and pitting corrosion to mechanical equipment is caused, and the service life of the mechanical equipment is further influenced. There are many measures to prevent and control oil contamination, among which fine filtration of lubricating oil using high-precision lubricating oil system filters is the most effective method. The lubricating oil filtering device is used for filtering pollutants generated by abrasion and corrosion of moving parts or brought into the system from the outside, so that the pollution level of an engine lubricating system is ensured, the system performance is prevented from being reduced or the function is lost due to high-precision matching with even parts jamming or pipeline blockage, and the system reliability is ensured. The filter paper layer is a core technology in the filter element, and is generally prepared from glass fibers, but the glass fibers are easy to be dispersed by a working fluid medium due to the poor bonding strength between the glass fibers. Therefore, the filter material can be improved in physical properties and application properties after the glass fiber is modified by the reinforcing resin so as to meet the processing application requirements.
In recent years, with the continuous increase of the running speed of vehicles, the service temperature of the lubricating oil system is gradually increased, especially in some special environments or abnormal service environments, the short-term temperature can reach more than 220 ℃, and higher requirements are put on the high-temperature resistant oil liquid performance of filter materials and combined resins. On the other hand, the cylinder folding filter element produced during manufacturing of the lubricating oil filter element can greatly improve the effective filtering area and the dirt-receiving capacity, and the shape, indentation pressure and depth of the folds are very important to the filtering effect of the formed filter in the fold design, and the filter paper layer acted by the resin has bending processability and can prevent collapse in practical application. In addition, the filter media is subject to the pulse effects of circulation flow, start-up, impact and vibration, which requires that the reinforcing resin should have excellent toughness in addition to high Wen Youye resistance, adhesion and strength properties to ensure that the filter media meets pleating requirements and the pulse effects of the application process.
The traditional reinforced resin of the lubricating oil filter glass fiber filter material is mostly thermoplastic acrylic resin, and has the advantages of good water and chemical resistance, easy processing and forming, convenient construction and environmental protection. One layer of the filter media reported in US 2015360156 is obtained by impregnating glass fibers with 5% thermoplastic acrylic resin HYCAR 26120 (Lubrizol); the use of a reinforced resin system of thermoplastic acrylic acid Eco32S (Rohm & Haas) mixed with thermosetting acrylic acid HF-05A (Rohm & Haas) at a 1:1 is also reported in foreign patent WO 2011087840; the reinforced resin reported in chinese patent CN 109930425 consists of an acrylic emulsion and a curing agent PF 7302B; another chinese patent CN 103191605 also employs a reinforced resin system of thermoplastic and thermosetting acrylic resins in a 1:1 composition. However, the thermoplastic acrylic resin has low crosslinking degree, so that the resin is swelled and softened by oil liquid at high temperature, and the filter material structure is damaged; even the addition of thermosetting resins or other crosslinker systems does not solve this problem. In order to solve the problem of high temperature resistance, chinese patent CN 110066359 can show good performance after being soaked in oil liquid at 150 ℃ by preparing water-soluble thermosetting acrylic resin, but the curing temperature of the system is high, and the system is easy to age under the working condition of exceeding 150 ℃, the strength is reduced, and the pulse resistance is reduced. In summary, although acrylic resin is the most widely used resin for filtering glass fiber filter materials of lubricating oil at present, products at home and abroad cannot meet the use of the filter element in the environment of 220 ℃.
Phenolic resins and epoxy resins are two important thermosetting reinforcing resins. The glass fiber filter material has excellent adhesive property, strength property, high temperature resistance and solvent resistance, and is also an excellent reinforced resin system of the glass fiber filter material. Attempts were made to impregnate glass fibers with phenolic resin to obtain oil filter papers as in the examples of patent CN 105233569 and patent WO 2016040292. However, phenolic resin on the market is mainly solvent type product, potential safety hazard exists in the production and processing process, and free phenol and formaldehyde exist in the product, so that the environment-friendly requirement is not met. In addition, phenolic resin also has high curing temperature and high brittleness after curing, which leads to poor processability of glass fiber paper products, so the application of phenolic resin reinforced lubricating oil filter paper has been recently reported. The rigid skeleton and the ether bond structure of the epoxy resin endow the epoxy resin with good heat resistance and oil resistance, and the epoxy resin is subjected to waterborne design and also has safety and environmental protection, so that the epoxy resin is used as reinforcing resin for meeting the high temperature resistance requirement of the filter material in some foreign products at present, and the chemical resistance and physical properties of the filter material can be improved to a certain extent. However, the toughness of the epoxy resin system is poor, so that the strength of the filter paper after bending is reduced, and the processing technology requirements cannot be met. The reinforcing resin reported in US 2012248034 is obtained by curing 75% of toughened epoxy resin EPIREZ 5520W60 (Hexion) and 25% of amine curing agent EPIKURE 8537WY60 (Hexion) at 105-120 ℃, but the structure, composition or preparation method of the modified epoxy resin is not described, and the processability of the treated glass fiber product is still difficult to meet pleating requirements, so that the glass fiber product treated with the epoxy resin is mainly applied to a wound filter.
With the change of the application range and the working environment of the lubricating oil system, the requirements of higher (220 ℃) on the high-temperature resistant oil liquid performance and the bonding performance of the reinforced resin are raised, and the currently disclosed filter material products or reinforced resin cannot meet the practical application processing requirements, so that an environment-friendly reinforced resin system capable of resisting higher-temperature lubricating oil and improving the processing performance of the reinforced filter material is needed.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides an organosilicon/polyurethane/epoxy resin composite resin emulsion. Firstly, polyurethane with excellent oil resistance and elasticity is selected as a toughening resin system; secondly, introducing an organosilicon structure chain segment with excellent high temperature resistance into the flexible chain segment of polyurethane so as to further improve the high temperature resistance; finally, epoxy resin with excellent high temperature resistance, bonding strength and chemical resistance is continuously introduced into the resin system structure, and finally the organosilicon/polyurethane/epoxy resin composite resin system is formed. The composite resin system can simultaneously have the excellent performances of epoxy resin, polyurethane and organic silicon materials, and can make up the defects of the epoxy resin, polyurethane and organic silicon materials. In addition, the hydrophilic polyethylene glycol soft chain segment and the hydrophilic chain extender with hydrophilic groups are introduced into the composite resin system, so that the composite resin can be watered under the combined action of the hydrophilic polyethylene glycol soft chain segment and the hydrophilic chain extender, and the composite resin becomes an environment-friendly water-based resin system. After the organosilicon/polyurethane/epoxy resin composite emulsion prepared by the invention is applied to the impregnation of glass fiber filter materials, the filter materials are endowed with excellent tensile strength and retention rate, so that the requirements of processing and pleating the reinforced filter materials can be met, the reinforced filter materials have excellent oil resistance and high temperature resistance, and the working condition application requirements of 220 ℃ high-temperature lubricating oil can be met.
In order to achieve the above object, the present invention adopts the following technical scheme:
the invention provides a preparation method of an organosilicon/polyurethane/epoxy resin composite emulsion, which is prepared by the following steps:
uniformly stirring dehydrated polyethylene glycol, hydroxyl silicone oil and metered diisocyanate in a reaction kettle provided with a stirring device, a condensing device, a nitrogen protection device and a temperature control device, and heating to 70-80 ℃ at room temperature for reacting for 2-4 hours to prepare an organosilicon/polyurethane prepolymer;
adding a metered hydrophilic chain extender, heating to 75-85 ℃ and reacting for 1-3 hours to prepare a hydrophilic organosilicon/polyurethane prepolymer;
III, adding metered epoxy resin and diluent, heating to 80-90 ℃ for reaction for 4-6 hours, and preparing an organosilicon/polyurethane/epoxy resin composite resin system;
IV, cooling to 40-50 ℃, adding a neutralizing agent, and uniformly stirring;
v, slowly adding deionized water (2-4 times of the mass of the composite resin) into a reaction system under stirring at 800-3000rpm to form organosilicon/polyurethane/epoxy resin composite emulsion;
vacuum distilling to remove most of the diluted solvent;
the organosilicon/polyurethane/epoxy resin composite emulsion can be obtained after the steps are completed.
Further, the diisocyanate is an aliphatic or alicyclic isocyanate monomer containing two-NCO groups in the structure.
Preferably, the diisocyanate is selected from one or more than two of isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), 1, 4-cyclohexane diisocyanate (CHDI), trimethyl-1, 6-hexamethylene diisocyanate (TMHDI) and cyclohexanedimethylene diisocyanate (HXDI) in any proportion.
Further, the molecular weight of the polyethylene glycol ranges from 800 to 3000. Preferably, the polyethylene glycol has a molecular weight of 1000 to 2000.
Further, the molecular weight of the hydroxyl silicone oil ranges from 500 to 2000. Preferably, the molecular weight of the hydroxy silicone oil is 800-1500.
Further, the molar ratio of the polyethylene glycol to the hydroxyl silicone oil is 4:1-9:1. Preferably, the molar ratio of polyethylene glycol to hydroxy silicone oil is 4:1-6:1.
Further, the molar ratio of the total amount of the polyethylene glycol and the hydroxyl silicone oil to the diisocyanate is 1:3-1:4. Preferably, the molar ratio of the total amount of polyethylene glycol and hydroxy silicone oil to diisocyanate is 1:3.5-1:3.8.
Further, the hydrophilic chain extender is carboxylic acid or sulfonic acid hydrophilic chain extender containing two-OH groups in the structure, and specifically is one of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, 1, 4-butanediol-2-sulfonic acid and 1, 2-dihydroxyl-3-propane sulfonic acid.
Preferably, the hydrophilic chain extender is selected from one of 2, 2-dimethylolpropionic acid and 2, 2-dimethylolbutyric acid.
Further, the molar ratio of the hydrophilic chain extender to the diisocyanate is 1:3-1:7. Preferably, the molar ratio of hydrophilic chain extender to diisocyanate is from 1:4 to 1:6.
Further, the epoxy resin is bisphenol A or bisphenol F epoxy resin with the following molecular structural formula:
wherein n is 1 The value of (a) is in the range of 0.85-1.43 (the epoxy value is 0.27-0.34), and n 2 The value of (a) is in the range of 0.95-1.35 (the epoxy value is 0.30-0.36). Preferably n 1 The value of (a) is 1.03-1.34 (the epoxy value is 0.28-0.32), n 2 The value of (a) is 1.07-1.28 (the epoxy value is 0.31-0.34).
Further, the mass ratio of the epoxy resin to the hydrophilic organosilicon/polyurethane prepolymer is 0.8:1-1.4:1. Preferably, the mass ratio of the epoxy resin to the hydrophilic silicone/polyurethane prepolymer is 1.0:1 to 1.2:1.
Further, the diluent is butanone, and the addition amount of the diluent is 40-100% of the mass of the epoxy resin. Preferably, the diluent is added in an amount of 60% -80% of the mass of the epoxy resin.
Further, the neutralizing agent is one or more than two of N, N-dimethylethanolamine, triethylamine and sodium hydroxide in any proportion. Preferably, triethylamine is used as the neutralizing agent.
Further, the molar ratio of the neutralizing agent to the hydrophilic chain extender is 1.1:1-1.4:1. Preferably, the molar ratio of neutralizing agent to hydrophilic chain extender is 1.2:1 to 1.3:1.
The invention provides the organosilicon/polyurethane/epoxy resin composite emulsion prepared by the preparation method.
The invention also provides a method for applying the organosilicon/polyurethane/epoxy resin composite emulsion to the lubricating oil glass fiber filter material. Specifically, after the organosilicon/polyurethane/epoxy resin composite emulsion is diluted by deionized water, a metered aqueous curing agent is added to form a reinforced resin impregnating solution which is used for impregnating glass fiber base paper, so that the high-performance glass fiber filter material for lubricating oil filtration is prepared. The preparation method comprises the following steps:
diluting the organosilicon/polyurethane/epoxy resin composite emulsion with deionized water, and adding a metered aqueous curing agent to form a reinforced resin impregnating solution;
II, dipping the glass fiber base paper into the reinforced resin dipping liquid; drying at 80-100deg.C to form glass fiber filter material, wherein the sizing amount of the reinforcing resin impregnating solution is 5.0+ -0.5% based on the weight of glass fiber base paper;
III, pleating the glass fiber filter material into a filter element, drying and curing for 15-30min at 110-150 ℃.
Further, the aqueous curing agent is one of an aqueous polyamide curing agent or an aqueous polyether amine curing agent. Preferably, the aqueous curing agent is an aqueous polyamide curing agent.
Further, the organosilicon/polyurethane/epoxy resin composite emulsion and the water-based curing agent are compounded according to the epoxy equivalent equal to the active hydrogen equivalent.
The glass fiber filter material for filtering the lubricating oil, which is prepared by the method, has excellent comprehensive performance, maintains excellent tensile strength and retention rate of the filter material, and has oil resistance, high temperature resistance, bonding performance and high toughness.
The beneficial technical effects of the invention are as follows:
(1) The organosilicon/polyurethane/epoxy resin composite emulsion is a uniform composite resin system formed by combining three systems of organosilicon, polyurethane and epoxy resin through chemical bonds. The specific expression is as follows: firstly, polyethylene glycol and hydroxyl silicone oil are blended, and terminal-OH groups of the polyethylene glycol and hydroxyl silicone oil are simultaneously reacted with-NCO groups of diisocyanate to generate terminal-NCO group type organosilicon/polyurethane prepolymer, and the process method can overcome the condition that phase separation is possibly caused by poor compatibility of hydrophobic silicone oil and hydrophilic polyethylene glycol in the system, so that a uniform system is formed; then, by strictly controlling the number of hydroxyl groups in bisphenol epoxy resin, which are subjected to grafting reaction with the prepolymer, the formed organosilicon/polyurethane/epoxy resin composite system combined through chemical bonds is ensured, the gel phenomenon is avoided in the reaction process, and the stability of the composite system is ensured. Finally, the carboxyl is neutralized to endow hydrophilic performance, so that the toughness and water solubility of the epoxy resin are doubly modified. Therefore, the organosilicon/polyurethane/epoxy resin composite resin system can be dissolved in water and simultaneously has excellent oil resistance and elasticity of polyurethane, high temperature resistance and toughness of the organosilicon system, and high temperature resistance, oil resistance and adhesion of the epoxy resin system.
(2) The glass fiber filter material reinforced by the organic silicon/polyurethane/epoxy resin composite emulsion can meet the pleating processing requirement of the filter material and the application requirement of the filter material under the working condition of high-temperature lubricating oil.
(3) The organic silicon/polyurethane/epoxy resin composite emulsion is an environment-friendly product after solvent is removed by a reduced pressure distillation method, and can meet the environment-friendly requirement of glass fiber filter materials in the sizing and processing processes.
Drawings
The present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a process flow of the organosilicon/polyurethane/epoxy resin composite emulsion, a preparation method and application thereof.
Fig. 2 is an SEM image (magnified 1000 times) of a glass fiber base paper.
Fig. 3a to 3f are SEM pictures (magnified 1000 times) of high performance glass fiber filter media for filtering lubricating oil (silicone/polyurethane/epoxy resin composite emulsions of examples 1 to 6) prepared in examples 7 to 12, respectively.
Fig. 4 is an SEM image (magnified 1000 times) of the high performance glass fiber filter media for filtering lubricating oil (silicone/polyurethane/epoxy resin composite emulsion of comparative example 2) prepared in comparative example 8.
Fig. 5 is an SEM image (magnified 1000 times) of a high performance glass fiber filter material for filtering lubricating oil (a water-soluble thermosetting acrylic resin described in patent CN 110066359A) prepared in comparative example 9.
Fig. 6 is an SEM image (magnified 1000 times) of a high performance glass fiber filter material (commercially available aqueous epoxy resin) for filtering lubricating oil prepared in comparative example 10.
Detailed Description
An organosilicon/polyurethane/epoxy resin composite emulsion, and a preparation method and application thereof are further described below with reference to specific examples. It will be understood by those skilled in the art that these examples are illustrative of the present invention, and the scope of the present invention is not limited thereto.
The experimental methods in the following examples are conventional methods unless otherwise specified. The raw materials, reagent materials and the like used in the examples described below are commercially available products unless otherwise specified.
In the following examples, the aqueous curing agent used for the silicone/polyurethane/epoxy composite emulsion is a commercially available aqueous polyamide curing agent.
Examples 1 to 6
Examples 1-6 prepared an organosilicon/polyurethane/epoxy resin composite emulsion, the raw material composition is shown in table 1, the process flow is shown in figure 1, and the preparation method comprises the following steps:
uniformly stirring dehydrated polyethylene glycol, hydroxyl silicone oil and diisocyanate in a reaction kettle provided with a stirring device, a condensing device, a nitrogen protection device and a temperature control device, and heating to 70-80 ℃ at room temperature for reacting for 2-4 hours to prepare an organosilicon/polyurethane prepolymer;
II, adding a hydrophilic chain extender, heating to 75-85 ℃ and reacting for 1-3 hours to prepare a hydrophilic organosilicon/polyurethane prepolymer;
III, adding epoxy resin and butanone, and heating to 80-90 ℃ to react for 4-6 hours to prepare an organosilicon/polyurethane/epoxy resin composite resin system;
IV, cooling to 40-50 ℃, adding triethylamine, and uniformly stirring;
v, slowly adding enough deionized water (2-4 times of the mass of the composite resin) into the reaction system under the stirring condition of 2000rpm to form organosilicon/polyurethane/epoxy resin composite emulsion, and continuing stirring for 1-2 hours after the phase inversion is completed;
VI, distilling under reduced pressure at 60 ℃ and negative pressure of-0.08 Mpa to remove butanone as a diluent solvent;
the organosilicon/polyurethane/epoxy resin composite emulsion can be obtained after the steps are completed, and the results are shown in Table 1.
Table 1 raw material compositions of examples 1 to 6 organosilicon/polyurethane/epoxy resin composite emulsions
As is clear from Table 1, examples 1 to 6 all formed stable and bluish emulsions within the scope of the present invention. The hydrophilic chain extenders of examples 1 to 6 were replaced with 1, 4-butanediol-2-sulfonic acid, 1, 2-dihydroxy-3-propane sulfonic acid, and silicone/polyurethane/epoxy resin composite emulsions satisfying the above requirements were also obtained.
Comparative examples 1 to 6
Comparative examples 1 to 6 were prepared as silicone/polyurethane/epoxy resin composite emulsions, the composition of the raw materials is shown in Table 2, and the preparation was carried out in the same procedure and method as in examples 1 to 6, and the results are shown in Table 2.
Table 2 raw material compositions of the Silicone/polyurethane/epoxy resin composite emulsions of comparative examples 1 to 6
As can be seen by comparison with examples 1 to 6, comparative example 1 uses a small molecular weight polyethylene glycol, and cannot form an emulsion; comparative example 2, which does not contain a silicone component, forms a stable emulsion but has poor oil resistance at 220 c (see comparative example 8 of table 3 below); the amount of diisocyanate used in comparative example 3 was too low to form an emulsion; the comparative example 4 has little hydrophilic chain extender usage, and forms unstable emulsion; comparative example 5 epoxy resin has a high epoxy value and the composite resin system gels; the amount of the neutralizer used in comparative example 6 is small, the formed emulsion is unstable, and the layering phenomenon of the system occurs. It was found that the silicone/polyurethane/epoxy resin composite emulsion having excellent stability could not be formed without the method of the present invention.
Examples 7 to 12
Examples 7 to 12 high performance glass fiber filter media for lubricating oil filtration were prepared using the silicone/polyurethane/epoxy resin composite emulsions of examples 1 to 6.
The organic silicon/polyurethane/epoxy resin composite emulsions prepared in the above examples 1 to 6 were diluted with deionized water, and then added with a metered aqueous curing agent to form a reinforced resin impregnating solution, which was used to impregnate glass fiber base paper (model 8510, made up of glass wool and chopped glass fibers, manufactured by Guangzhou Hua chemical material science and technology development Co., ltd.) to prepare a high-performance glass fiber filter material for lubricating oil filtration. The preparation method comprises the following steps:
the silicone/polyurethane/epoxy resin composite emulsions of examples 1 to 6 were diluted with deionized water, respectively, and a metered aqueous curing agent (Westlake company, model EPIKURETMCuring Agent 8537-WY-60, active hydrogen equivalent 174 g/eq) was added according to table 3 to prepare a reinforcing resin impregnating solution. Wherein, the reinforced resin impregnating solution is compounded according to the theoretical value that the epoxy equivalent is equal to the active hydrogen equivalent by the organosilicon/polyurethane/epoxy resin composite emulsion and the water-based curing agent.
Table 3 compounding ratio of organosilicon/polyurethane/epoxy resin composite emulsion and Water-based curing agent
| Organosilicon/polyurethane/epoxy resin composite emulsion dosage ratio | Water-based curing agent dosage ratio | |
| Example 7 | 78.4％ | 21.6％ |
| Example 8 | 77.9％ | 22.1％ |
| Example 9 | 79.2％ | 20.8％ |
| Example 10 | 78.2％ | 21.8％ |
| Example 11 | 77.3％ | 22.7％ |
| Example 12 | 77.3％ | 22.7％ |
II, respectively soaking the glass fiber base paper in the reinforced resin impregnating solution; and drying at 80-100 deg.c to form glass fiber filtering material. Wherein, the sizing amount of the reinforced resin impregnating solution is 5.0+/-0.5 percent by taking the weight of the glass fiber base paper as the reference;
and III, pleating the glass fiber filter material to obtain a filter element, drying and curing for 15min at 120 ℃.
The high performance glass fiber filter material prepared above was observed by scanning electron microscopy, and the electron microscopy scanning photographs of examples 7 to 12 are shown in fig. 3a to 3f. Fig. 2 is an SEM picture of glass fiber base paper, and compared with fig. 2, it can be seen that the high-performance glass fiber filter material obtained by applying the organosilicon/polyurethane/epoxy resin composite emulsion on the glass fiber base paper according to the embodiment of the invention can maintain an excellent pore structure, and no obvious pore blocking phenomenon occurs, so that the filtration performance of the filter material is not obviously affected by the organosilicon/polyurethane/epoxy resin composite emulsion.
Comparative example 7
Comparative example 7 an organosilicon/polyurethane/epoxy resin composite emulsion was prepared, the raw material composition of which is as in example 1 of table 1, according to the same procedure and method as in examples 1 to 6, except that:
polyethylene glycol, hydroxyl silicone oil, a hydrophilic chain extender and diisocyanate are stirred uniformly, and the temperature is raised to 75 ℃ at room temperature to react for 4 hours, so that a hydrophilic organosilicon/polyurethane prepolymer is prepared;
the hydrophilic chain extender is added in step I.
In the process of preparing the hydrophilic organosilicon/polyurethane prepolymer, the organosilicon/polyurethane/epoxy resin composite emulsion prepared in the comparative example can quickly generate a gel phenomenon, and cannot be subjected to the next reaction. It was found that the silicone/polyurethane/epoxy resin composite emulsion having excellent stability could not be formed without the method of the present invention.
Comparative example 8
The high-performance glass fiber filter material for filtering lubricating oil is prepared in the embodiment. The high-performance glass fiber filter media for filtering lubricating oil according to this comparative example was prepared by substantially the same procedure as in examples 7 to 12, except that:
the organosilicon/polyurethane/epoxy resin composite emulsion used is that obtained in comparative example 2. In particular, comparative example 2 does not contain a silicone resin, referred to as a polyurethane/epoxy resin composite emulsion; wherein, the compounding ratio of the polyurethane/epoxy resin composite emulsion and the water-based curing agent is 77.9 percent: 22.1%;
and II, dipping the glass fiber base paper into the reinforced resin dipping liquid to obtain the high-performance glass fiber filter material of comparative example 8 (polyurethane/epoxy resin composite emulsion).
The high-performance glass fiber filter material prepared by the method is observed through a scanning electron microscope, and an electron microscope scanning photo of comparative example 8 is shown in fig. 4.
As can be seen from fig. 4, the high-performance glass fiber filter material obtained by applying the polyurethane/epoxy resin composite emulsion of comparative example 2 to glass fiber base paper can maintain an excellent pore structure, and no obvious pore blocking phenomenon occurs.
Comparative example 9
The high-performance glass fiber filter material for filtering lubricating oil is prepared in the embodiment. The high-performance glass fiber filter media for filtering lubricating oil according to this comparative example was prepared by substantially the same procedure as in examples 7 to 12, except that:
a water-soluble thermosetting acrylic resin (example 1) described in patent CN 110066359A is selected to replace the organosilicon/polyurethane/epoxy resin composite emulsion described in examples 7-12, and a curing agent is not used;
and II, immersing the glass fiber base paper in the reinforced resin impregnating solution to obtain the high-performance glass fiber filter material of comparative example 9 (water-soluble thermosetting acrylic resin).
The high-performance glass fiber filter material prepared by the method is observed through a scanning electron microscope, and an electron microscope scanning photo of a comparative example 9 is shown in fig. 5.
As can be seen from fig. 5, the high-performance glass fiber filter material obtained by applying the water-soluble thermosetting acrylic resin disclosed in patent CN 110066359A on glass fiber base paper can maintain an excellent pore structure, and no obvious pore blocking phenomenon occurs.
Comparative example 10
The high-performance glass fiber filter material for filtering lubricating oil is prepared in the embodiment. The high-performance glass fiber filter media for filtering lubricating oil according to this comparative example was prepared by substantially the same procedure as in examples 7 to 12, except that:
a commercially available waterborne epoxy resin (Westlake Co., model EPI-REZ) was used TM Resin 5520-W-60 with an epoxy equivalent of 480-560 g/eq) in place of the silicone/polyurethane/epoxy composite emulsions described in examples 7-12; wherein, the compounding ratio of the aqueous epoxy resin and the aqueous curing agent is 75.0 percent: 25.0%;
and II, immersing the glass fiber base paper in a reinforcing resin impregnating solution to obtain the high-performance glass fiber filter material of comparative example 10 (commercial waterborne epoxy resin).
The high-performance glass fiber filter material prepared above was observed by a scanning electron microscope, and the electron microscope scanning photograph of comparative example 10 is shown in fig. 6.
As can be seen from fig. 6, the high-performance glass fiber filter material obtained by applying the commercial aqueous epoxy resin to the glass fiber base paper can maintain an excellent pore structure, and no obvious pore blocking phenomenon occurs.
Test example 1
The pleating processability of the high-performance glass fiber filter media for filtration of lubricating oil obtained in examples 7 to 12 and the high-performance glass fiber filter media for filtration of lubricating oil obtained in comparative examples 8 to 10 were measured.
The glass fiber base paper (model 8510, made up of glass wool and chopped glass fibers, manufactured by Guangzhou Hua chemical materials science and technology development Co., ltd.), the high performance glass fiber filter materials for lubricating oil filtration prepared in examples 7 to 12 and comparative examples 8 to 10 were measured, and the basis weight, tensile strength and stiffness before pleating, and the tensile strength after pleating were measured. The detection results are shown in Table 4.
Table 4 results of pleating processability test of high performance glass fiber filter media for filtering lubricating oil of examples and comparative examples
Pleating processability was evaluated by: reference to the national standard (GB/T17939-2015) is specifically appendix A.3.6 (flex resistance). The filter paper was cut into test pieces 300mm long and 150mm wide in the longitudinal direction. And in the range of the length of the sample (250+/-12) mm, pulling the sample to bend on a thin shaft which is vertical to the diameter of 5mm, wherein the bending radian is 180 degrees, and the bending times are 1 time. After testing, no cracking, breaking, crazing or delamination on the filter material was considered to pass the test.
Determination of stiffness was tested with a bending stiffness tester (model: 79-25-00-0002, TMI Co., U.S.) against national standards (GB/T22364-2018); measurement of tensile Strength the tensile Strength was measured with a tensile Strength apparatus (model: CE062, swedish L & W Co.) with reference to the national standard (GB/T12914-2018).
As can be seen from Table 4, the high performance glass fiber filter material obtained by applying the organosilicon/polyurethane/epoxy resin composite emulsion of examples 7-12 to glass fiber base paper has tensile strength and retention rate which are even higher than those of the (water-soluble thermosetting acrylic resin) glass fiber filter material of comparative example 9 after pleating process treatment, and the retention rate of example 8 reaches 64.94%, because polyethylene glycol is used as a toughening chain segment, toughness of the glass fiber filter material after resin reinforcement is effectively improved, stress can be dispersed when the glass fiber filter material is bent, thereby effectively inhibiting crack propagation and reducing breaking degree of fine fibers; compared with comparative example 8, the tensile strength and the retention rate of the high-performance glass fiber filter material obtained by the organic silicon/polyurethane/epoxy resin composite emulsion acting on glass fiber base paper after pleating are equivalent to those of the (polyurethane/epoxy resin composite emulsion) high-performance glass fiber filter material described in comparative example 8, which shows that the tensile strength of the glass fiber filter material is not influenced by the dosage of the organic silicon resin; compared with comparative example 10, the tensile strength and the retention rate of the high-performance glass fiber filter material obtained by applying the organosilicon/polyurethane/epoxy resin composite emulsion to glass fiber base paper after pleating are obviously better than those of the (commercial waterborne epoxy resin) high-performance glass fiber filter material described in comparative example 10.
Test example 2
High-performance glass fiber Filter Material for Lubricant filtration obtained in examples 7 to 12 and measurement of high-temperature resistance Lubricant Performance of high-performance glass fiber Filter Material for Lubricant filtration obtained in comparative examples 8 to 10
The high performance glass fiber filters for filtration of lubricating oil prepared in examples 7 to 12 and comparative examples 8 to 10 were measured, and the glass fiber filters before and after pleating were immersed in an aviation lubricating oil at 220℃respectively, and the tensile strength of the glass fiber filters after immersing in the high temperature lubricating oil was measured. The detection results are shown in Table 5.
Table 5 results of high temperature resistant lubricating oil property test of high performance glass fiber filter media for lubricating oil filtration of each of examples and comparative examples
The high temperature resistant lubricating oil performance was evaluated by: and (3) soaking glass fiber filter paper in aviation lubricating oil with the oil temperature of 220 ℃ for 48 hours, fully exposing two sides of the glass fiber filter paper to the oil, taking out the glass fiber filter paper, gently wiping off the surface lubricating oil by using the filter paper, washing the residual lubricating oil by using petroleum ether for three times, and finally drying the glass fiber filter paper in an oven with the temperature of 80 ℃ until the weight is constant, and performing performance test.
Measurement of tensile Strength the tensile Strength was measured with a tensile Strength apparatus (model: CE062, swedish L & W Co.) with reference to the national standard (GB/T12914-2018).
As can be seen from Table 5, the high performance glass fiber filter material obtained by applying the organosilicon/polyurethane/epoxy resin composite emulsion of examples 7-12 to glass fiber base paper has tensile strength and retention rate of 90% or more before and after oil immersion, which indicates that the glass fiber filter material has excellent high temperature resistant oil liquid performance; after passing the high-temperature-resistant oil liquid test, the pleated glass fiber filter material still has higher retention rate of tensile strength, which indicates that the filter material can keep stable structure and strength after being soaked in the high-temperature oil liquid for a long time even after being pleated. Compared with the (polyurethane/epoxy resin composite emulsion) high-performance glass fiber filter material in comparative example 8, the tensile strength and the retention rate of the composite emulsion without adding the organic silicon resin after oil immersion are obviously reduced, the retention rate is only 61.08%, which indicates that the addition of the organic silicon resin can effectively improve the high-temperature oil resistance of the glass fiber filter material; after the pleated glass fiber filter material passes through the high-temperature-resistant oil liquid test, the tensile strength is further reduced, and the stability of the structure and the strength cannot be maintained. The tensile strength and retention rate before and after oil immersion were very low compared with those of the (water-soluble thermosetting acrylic resin) high-performance glass fiber filter material described in comparative example 9, and the tensile strength and retention rate after passing the high-temperature oil resistance test of the pleated glass fiber filter material were further reduced, indicating that the (water-soluble thermosetting acrylic resin) high-performance glass fiber filter material cannot withstand the high-temperature oil environment of 220 ℃. Compared with the (commercially available pure water epoxy resin) high-performance glass fiber filter material in comparative example 10, the tensile strength and the retention rate of the glass fiber filter material before and after oil immersion can reach more than 90%, which shows that the glass fiber filter material has excellent high-temperature oil resistance; however, after the pleated glass fiber filter material passes the high-temperature-resistant oil liquid test, the tensile strength retention rate is 0, which indicates that the structure and strength of the (commercially available pure water epoxy resin) high-performance glass fiber filter material cannot be kept stable after being pleated, and the glass fiber filter material is dispersed by a fluid medium in a high Wen Youye.
The above examples are only preferred embodiments of the present invention, and are merely for illustrating the present invention, not for limiting the present invention, and those skilled in the art should not be able to make any changes, substitutions, modifications and the like without departing from the spirit of the present invention.
Claims (10)
1. The preparation method of the organosilicon/polyurethane/epoxy resin composite emulsion comprises the following steps:
uniformly stirring dehydrated polyethylene glycol, hydroxyl silicone oil and metered diisocyanate in a reaction kettle provided with a stirring device, a condensing device, a nitrogen protection device and a temperature control device, and heating to 70-80 ℃ at room temperature for reacting for 2-4 hours to prepare an organosilicon/polyurethane prepolymer;
adding a metered hydrophilic chain extender, heating to 75-85 ℃ and reacting for 1-3 hours to prepare a hydrophilic organosilicon/polyurethane prepolymer;
III, adding metered epoxy resin and diluent, heating to 80-90 ℃ for reaction for 4-6 hours, and preparing an organosilicon/polyurethane/epoxy resin composite resin system;
IV, cooling to 40-50 ℃, adding a neutralizing agent, and uniformly stirring;
v, adding deionized water into the reaction system under stirring at 800-3000rpm to form organosilicon/polyurethane/epoxy resin composite emulsion;
vacuum distilling to remove most of the diluted solvent;
the organosilicon/polyurethane/epoxy resin composite emulsion can be obtained after the steps are completed.
2. The method for preparing the organosilicon/polyurethane/epoxy resin composite emulsion according to claim 1, wherein in the step I, the diisocyanate is an aliphatic or alicyclic isocyanate monomer containing two-NCO groups in the structure; the molecular weight of the polyethylene glycol ranges from 800 to 3000; the molecular weight of the hydroxyl silicone oil ranges from 500 to 2000; the mol ratio of polyethylene glycol to hydroxyl silicone oil is 4:1-9:1; the molar ratio of the total dosage of the polyethylene glycol and the hydroxyl silicone oil to the diisocyanate is 1:3-1:4.
3. The method for preparing the organosilicon/polyurethane/epoxy resin composite emulsion according to claim 1, wherein in the step II, the hydrophilic chain extender is carboxylic acid or sulfonic acid hydrophilic chain extender containing two-OH groups in the structure; the molar ratio of the hydrophilic chain extender to the diisocyanate is 1:3-1:7.
4. The method for preparing an organosilicon/polyurethane/epoxy resin composite emulsion according to claim 1, wherein in the step iii, the epoxy resin is bisphenol a type or bisphenol F type epoxy resin having the following molecular structural formula:
wherein n is 1 The value of (2) is in the range of 0.85-1.43, n 2 The range of the value of (2) is 0.95-1.35.
5. The method for preparing the organosilicon/polyurethane/epoxy resin composite emulsion according to claim 1, wherein in the step III, the mass ratio of the epoxy resin to the hydrophilic organosilicon/polyurethane prepolymer is 0.8:1-1.4:1; the diluent is butanone, and the addition amount of the diluent is 40-100% of the mass of the epoxy resin.
6. The method for preparing the organosilicon/polyurethane/epoxy resin composite emulsion according to claim 1, wherein in the step IV, the neutralizing agent is one or more than two of N, N-dimethylethanolamine, triethylamine and sodium hydroxide in any proportion; the molar ratio of the neutralizing agent to the hydrophilic chain extender is 1.1:1-1.4:1.
7. An organosilicon/polyurethane/epoxy resin composite emulsion prepared by the preparation method according to any one of claims 1-6.
8. The use of a silicone/polyurethane/epoxy composite emulsion according to claim 7, wherein the silicone/polyurethane/epoxy composite emulsion is applied to a lubricating oil glass fiber filter material; specifically, after the organosilicon/polyurethane/epoxy resin composite emulsion is diluted by deionized water, a metered aqueous curing agent is added to form a reinforced resin impregnating solution which is used for impregnating glass fiber base paper, so that the high-performance glass fiber filter material for lubricating oil filtration is prepared by the following steps:
diluting the organosilicon/polyurethane/epoxy resin composite emulsion of claim 7 with deionized water, and adding a metered aqueous curing agent to form a reinforced resin impregnating solution;
II, immersing the glass fiber base paper in the reinforced resin impregnating solution, and drying at 80-100 ℃ to form a glass fiber filter material, wherein the sizing amount of the reinforced resin impregnating solution is 5.0+/-0.5% based on the weight of the glass fiber base paper;
III, pleating the glass fiber filter material into a filter element, drying and curing for 15-30min at 110-150 ℃.
9. The use of an organosilicon/polyurethane/epoxy resin composite emulsion according to claim 8, wherein the aqueous curing agent is one of an aqueous polyamide curing agent or an aqueous polyether amine curing agent; the organosilicon/polyurethane/epoxy resin composite emulsion and the water-based curing agent are compounded according to the theoretical value that the epoxy equivalent is equal to the active hydrogen equivalent.
10. The high-performance glass fiber filter material for high-temperature resistant lubricating oil filtration obtained by the application according to claim 8 or 9.
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