CN109486457B - A kind of interlayer bonding material with high temperature resistance, high viscosity, high strength and high toughness and preparation method thereof - Google Patents
A kind of interlayer bonding material with high temperature resistance, high viscosity, high strength and high toughness and preparation method thereof Download PDFInfo
- Publication number
- CN109486457B CN109486457B CN201811219012.8A CN201811219012A CN109486457B CN 109486457 B CN109486457 B CN 109486457B CN 201811219012 A CN201811219012 A CN 201811219012A CN 109486457 B CN109486457 B CN 109486457B
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- China
- Prior art keywords
- parts
- aramid fiber
- epoxy resin
- heterocyclic aramid
- bonding material
- 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.)
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- 239000000463 material Substances 0.000 title claims abstract description 96
- 239000011229 interlayer Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 130
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 127
- 239000003822 epoxy resin Substances 0.000 claims abstract description 119
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 119
- 239000004814 polyurethane Substances 0.000 claims abstract description 79
- 229920002635 polyurethane Polymers 0.000 claims abstract description 79
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 35
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 27
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 polyethylene Polymers 0.000 claims abstract description 27
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 26
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004698 Polyethylene Substances 0.000 claims abstract description 21
- 229920000768 polyamine Polymers 0.000 claims abstract description 21
- 229920000573 polyethylene Polymers 0.000 claims abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 18
- 238000011282 treatment Methods 0.000 claims abstract description 17
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 43
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 29
- 229960001124 trientine Drugs 0.000 claims description 29
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 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 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 9
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims 4
- 238000001816 cooling Methods 0.000 claims 2
- 230000000052 comparative effect Effects 0.000 description 54
- 239000004760 aramid Substances 0.000 description 25
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 16
- 239000000835 fiber Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000000805 composite resin Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- ZHMRGFNMPNFNPW-UHFFFAOYSA-N 1,3-thiazole-2,5-diamine Chemical compound NC1=CN=C(N)S1 ZHMRGFNMPNFNPW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 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 3
- 239000010410 layer Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
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- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/341—Dicarboxylic acids, esters of polycarboxylic acids containing two carboxylic acid groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4057—Carbamates
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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Abstract
本发明公开了一种耐高温高粘高强高韧层间粘结材料及制备方法，该层间粘结材料以重量份数计，由以下原料制成：聚四氢呋喃醚二醇15～20份、异佛尔酮二异氰酸酯5～10份、丁二酸酐5～10份、二乙醇胺5～10份、三羟甲基丙烷4～8份、杂环芳纶纤维30～40份、环氧树脂100份、多乙烯多胺10～15份。该层间粘结材料的制备方法为制备脂肪族超支化聚氨酯、对杂环芳纶纤维表面处理、对杂环芳纶纤维进行表面接枝处理、通过超支化聚氨酯改性杂环芳纶纤维和环氧树脂制备超支化聚氨酯改性杂环芳纶纤维环氧树脂固化剂、向环氧树脂中添加制备的固化剂得到层间粘结材料。本发明的层间粘结材料具有高强度、高韧性、抗冲击等优异性能，制备工艺简单、反应过程可控。The invention discloses a high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material and a preparation method. The interlayer bonding material is prepared in parts by weight from the following raw materials: 15-20 parts of polytetrahydrofuran ether glycol, 5-10 parts of isophorone diisocyanate, 5-10 parts of succinic anhydride, 5-10 parts of diethanolamine, 4-8 parts of trimethylolpropane, 30-40 parts of heterocyclic aramid fiber, 100 parts of epoxy resin parts, 10-15 parts of polyethylene polyamine. The preparation method of the interlayer bonding material includes preparing aliphatic hyperbranched polyurethane, treating the surface of the heterocyclic aramid fiber, performing surface grafting treatment on the heterocyclic aramid fiber, modifying the heterocyclic aramid fiber by the hyperbranched polyurethane and The epoxy resin is used to prepare a hyperbranched polyurethane modified heterocyclic aramid fiber epoxy resin curing agent, and the prepared curing agent is added to the epoxy resin to obtain an interlayer bonding material. The interlayer bonding material of the invention has excellent properties such as high strength, high toughness, impact resistance, etc., the preparation process is simple, and the reaction process is controllable.
Description
技术领域technical field
本发明属于道路材料领域，涉及一种层间粘结材料，具体涉及一种耐高温高粘高强高韧层间粘结材料及制备方法。The invention belongs to the field of road materials, and relates to an interlayer bonding material, in particular to an interlayer bonding material with high temperature resistance, high viscosity, high strength and high toughness, and a preparation method.
背景技术Background technique
桥面铺装粘结层破坏是导致桥面铺装病害的一个主要原因，桥面铺装粘结的好坏直接影响行车的安全性、舒适性，甚至桥梁的使用寿命；良好的防水粘结层可以提高铺装层的抗剪切性能，减少铺装层产生推移、拥包、渗水等早期病害情况发生。环氧树脂具有优异的粘结性能以及高模量、高强度、耐化学性好等优点，在国内外在长期研究过程中发现环氧树脂在桥面防水、层间粘结等方面具有明显的优势并得到广泛应用。但随着超载、重载常态化对防水黏结材料提出更高的要求，以及环氧树脂本身存在脆性大和耐冲击性差的缺点，因此需对环氧树脂加以增韧增强使其具有更优异的性能。The damage of the bridge deck pavement adhesive layer is one of the main causes of the bridge deck pavement disease. The quality of the bridge deck pavement bonding directly affects the safety, comfort, and even the service life of the bridge; good waterproof bonding The layer can improve the shear resistance of the pavement layer, and reduce the occurrence of early diseases such as the pavement layer slipping, wrapping, and water seepage. Epoxy resin has excellent bonding properties, high modulus, high strength, good chemical resistance and other advantages. In the long-term research process at home and abroad, it has been found that epoxy resin has obvious advantages in bridge deck waterproofing and interlayer bonding. advantages and are widely used. However, with the normalization of overload and heavy load, higher requirements are placed on waterproof bonding materials, and the epoxy resin itself has the shortcomings of high brittleness and poor impact resistance, so epoxy resin needs to be toughened and strengthened to have better performance. .
发明内容SUMMARY OF THE INVENTION
针对现有技术中的缺陷和不足，本发明提供了一种耐高温高粘高强高韧层间粘结材料及制备方法，克服现有粘结材料韧性低、耐冲击性能差的缺陷。Aiming at the defects and deficiencies in the prior art, the present invention provides an interlayer bonding material with high temperature resistance, high viscosity, high strength and high toughness and a preparation method, which overcomes the defects of low toughness and poor impact resistance of the existing bonding material.
为达到上述目的，本发明采取如下的技术方案：To achieve the above object, the present invention adopts the following technical scheme:
一种耐高温高粘高强高韧层间粘结材料，制备该粘结材料的原料包括环氧树脂，还包括聚四氢呋喃醚二醇、异佛尔酮二异氰酸酯、丁二酸酐、二乙醇胺、三羟甲基丙烷、杂环芳纶纤维和多乙烯多胺。An interlayer bonding material with high temperature resistance, high viscosity, high strength and high toughness. Methylolpropane, Heterocyclic Aramid Fibers and Polyethylene Polyamines.
以重量份数计，由以下原料制成：聚四氢呋喃醚二醇(PTMG)15～20份、异佛尔酮二异氰酸酯(IP-DI)5～10份、丁二酸酐5～10份、二乙醇胺5～10份、三羟甲基丙烷4～8份、杂环芳纶纤维30～40份、环氧树脂100份、多乙烯多胺10～15份。In parts by weight, it is made from the following raw materials: 15-20 parts of polytetrahydrofuran ether glycol (PTMG), 5-10 parts of isophorone diisocyanate (IP-DI), 5-10 parts of succinic anhydride, 5-10 parts of ethanolamine, 4-8 parts of trimethylolpropane, 30-40 parts of heterocyclic aramid fiber, 100 parts of epoxy resin, and 10-15 parts of polyethylene polyamine.
本发明还具有如下技术特征：The present invention also has the following technical features:
可选地，以重量份数计，由以下原料制成：聚四氢呋喃醚二醇15～20份、异佛尔酮二异氰酸酯5～10份、丁二酸酐5～8份、二乙醇胺5～8份、三羟甲基丙烷4～6份、杂环芳纶纤维35份、环氧树脂100份、多乙烯多胺12份。Optionally, in parts by weight, it is made from the following raw materials: 15-20 parts of polytetrahydrofuran ether diol, 5-10 parts of isophorone diisocyanate, 5-8 parts of succinic anhydride, and 5-8 parts of diethanolamine parts, 4-6 parts of trimethylolpropane, 35 parts of heterocyclic aramid fibers, 100 parts of epoxy resin, and 12 parts of polyethylene polyamine.
可选地，以重量份数计，由以下原料制成：聚四氢呋喃醚二醇18份、异佛尔酮二异氰酸酯7份、丁二酸酐7份、二乙醇胺8份、三羟甲基丙烷5份、杂环芳纶纤维35份、环氧树脂100份、多乙烯多胺12份。Optionally, in parts by weight, it is made from the following raw materials: 18 parts of polytetrahydrofuran ether diol, 7 parts of isophorone diisocyanate, 7 parts of succinic anhydride, 8 parts of diethanolamine, 5 parts of trimethylolpropane parts, 35 parts of heterocyclic aramid fiber, 100 parts of epoxy resin, and 12 parts of polyvinylpolyamine.
可选地，所述的杂环芳纶纤维的结构式为：Optionally, the structural formula of the heterocyclic aramid fiber is:
其中：n取值范围为100～1000。Among them: n is in the range of 100 to 1000.
所述的杂环芳纶纤维为一种起始单体为2，5-二氨基噻唑和对苯二甲酸，通过高温溶液聚合法合成的一种五元含氮杂环聚芳酰胺，能溶解于二甲基亚砜和N，N-二甲基甲酰胺等有机溶剂，熔点大于310℃。Said heterocyclic aramid fiber is a kind of five-membered nitrogen-containing heterocyclic polyaromatic amide synthesized by high temperature solution polymerization with the starting monomers of 2,5-diaminothiazole and terephthalic acid, which can dissolve In organic solvents such as dimethyl sulfoxide and N,N-dimethylformamide, the melting point is higher than 310℃.
可选地，所述的环氧树脂为双酚A型环氧树脂E-44，其中，双酚A型环氧树脂E-44的环氧值为0.41～0.47eq/100g、环氧当量为212～244g/eq。Optionally, the epoxy resin is bisphenol A epoxy resin E-44, wherein the epoxy value of bisphenol A epoxy resin E-44 is 0.41-0.47eq/100g, and the epoxy equivalent is 212～244g/eq.
可选地，所述的多乙烯多胺为二乙烯三胺、三乙烯四胺或四乙烯五胺中任意一种或多种复合。Optionally, the polyethylene polyamine is a composite of any one or more of diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
在本发明中，聚四氢呋喃醚二醇的分子量Mn＝1000，聚合度n＝13.6。In the present invention, the molecular weight of the polytetrahydrofuran ether diol is Mn=1000, and the degree of polymerization is n=13.6.
本发明还提供了一种耐高温高粘高强高韧层间粘结材料的制备方法，该制备方法采用所述的耐高温高粘高强高韧层间粘结材料的原料，该方法包括以下步骤：The present invention also provides a method for preparing a high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material. The preparation method adopts the raw material of the high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material, and the method includes the following steps :
步骤一：制备脂肪族超支化聚氨酯：Step 1: Preparation of Aliphatic Hyperbranched Polyurethane:
以N，N-二甲基甲酰胺(DMF)作为溶剂，加入干燥后的聚四氢呋喃醚二醇、采用二月桂酸二丁基锡为催化剂，滴加异佛尔酮二异氰酸酯，在氮气气氛中，75℃下反应1.5h，得到—NCO封端的聚氨酯预聚体(PPU)；Using N,N-dimethylformamide (DMF) as a solvent, adding dried polytetrahydrofuran ether diol, using dibutyltin dilaurate as a catalyst, adding isophorone diisocyanate dropwise, in a nitrogen atmosphere, 75 React at ℃ for 1.5 h to obtain -NCO-terminated polyurethane prepolymer (PPU);
以甲醇作溶剂，冰水浴下加入丁二酸酐和二乙醇胺，氮气气氛中反应6h，干燥得4-(双(2-羟乙基)亚胺)-4-氧代丁酸(AB2)单体；继续将三羟甲基丙烷和上述4-(双(2-羟乙基)亚胺)-4-氧代丁酸(AB2)单体加入到反应釜中，以甲苯磺酸作催化剂，甲苯为带水剂，在120℃下酯化反应8h至无水生成，得到淡黄色黏稠液体即为超支化聚合物(HPAE)；Using methanol as a solvent, add succinic anhydride and diethanolamine in an ice-water bath, react in a nitrogen atmosphere for 6 h, and dry to obtain 4-(bis(2-hydroxyethyl)imine)-4-oxobutyric acid (AB2) monomer Continue to join trimethylolpropane and above-mentioned 4-(two (2-hydroxyethyl) imine)-4-oxobutyric acid (AB2) monomer in the reactor, make catalyzer with toluenesulfonic acid, toluene As a water-carrying agent, the esterification reaction is carried out at 120 ° C for 8 hours until anhydrous is formed, and a light yellow viscous liquid is obtained, which is a hyperbranched polymer (HPAE);
在上述制备好的聚氨酯预聚体(PPU)中加入制备的超支化聚合物HPAE，在氮气气氛中，75℃下反应4.5h，得到无色粘稠液体即为脂肪族超支化聚氨酯(HBPU)；Add the prepared hyperbranched polymer HPAE to the above prepared polyurethane prepolymer (PPU), and react in a nitrogen atmosphere at 75 ° C for 4.5 hours to obtain a colorless viscous liquid, which is aliphatic hyperbranched polyurethane (HBPU) ;
步骤二：杂环芳纶纤维表面处理：Step 2: Heterocyclic aramid fiber surface treatment:
将400目杂环芳纶纤维用丙酮超声清洗2h后烘干，再在质量浓度为20％、温度为40℃的磷酸溶液中浸泡，浸泡后在80℃下真空干燥12h，再加入到异佛尔酮二异氰酸酯的溶液中反应，用去离子清洗至中性并干燥后得到表面含有高活泼性的羟基—OH、异氰酸根基—NCO和氨基—NH2的表面处理的杂环芳纶纤维；The 400-mesh heterocyclic aramid fiber was ultrasonically cleaned with acetone for 2 hours, then dried, and then soaked in a phosphoric acid solution with a mass concentration of 20% and a temperature of 40 ° C. After soaking, it was vacuum-dried at 80 ° C for 12 hours, and then added to Yifo Reaction in the solution of ketone diisocyanate, cleaning with deionization to neutrality and drying to obtain surface-treated heterocyclic aramid fibers containing highly active hydroxyl-OH, isocyanato-NCO and amino-NH2 on the surface;
步骤三：杂环芳纶纤维表面接枝处理：Step 3: Surface Grafting Treatment of Heterocyclic Aramid Fiber:
将步骤一制备的脂肪族超支化聚氨酯(HBPU)加入反应釜中，用N，N-二甲基甲酰胺作稀释剂，加入上述步骤二经过表面处理的杂环芳纶纤维，80～90℃下经超声波处理后，在高速剪切的条件下反应5小时得到表面接枝超支化聚氨酯的杂环芳纶纤维，分离、提纯、干燥得超支化聚氨酯改性杂环芳纶纤维；Add the aliphatic hyperbranched polyurethane (HBPU) prepared in step 1 into the reaction kettle, use N,N-dimethylformamide as a diluent, add the surface-treated heterocyclic aramid fiber in the above step 2, 80～90℃ After ultrasonic treatment, react under high-speed shearing conditions for 5 hours to obtain the surface-grafted heterocyclic aramid fiber of hyperbranched polyurethane, and separate, purify and dry to obtain the hyperbranched polyurethane modified heterocyclic aramid fiber;
步骤四：环氧树脂固化剂的制备：Step 4: Preparation of epoxy resin curing agent:
将步骤三中得到的超支化聚氨酯改性杂环芳纶纤维和环氧树脂溶于丙二醇甲醚后，加入反应釜中与表面活性剂在70℃反应3.5h，再加入多乙烯多胺进行加成反应，添加丁基缩水甘油醚对加成物进行封端，反应结束后降温至50℃加入冰醋酸调节亲水亲油平衡，在减压条件下蒸馏出溶剂，即得超支化聚氨酯改性杂环芳纶纤维环氧树脂固化剂；After dissolving the hyperbranched polyurethane-modified heterocyclic aramid fiber and epoxy resin obtained in step 3 in propylene glycol methyl ether, it was added to the reaction kettle and reacted with the surfactant at 70 ° C for 3.5 hours, and then polyethylene polyamine was added. After the reaction is completed, butyl glycidyl ether is added to cap the adduct. After the reaction, the temperature is lowered to 50 °C and glacial acetic acid is added to adjust the hydrophilic-lipophilic balance. The solvent is distilled off under reduced pressure to obtain hyperbranched polyurethane modification. Heterocyclic aramid fiber epoxy resin curing agent;
步骤五：制备层间粘结材料：Step 5: Preparation of interlayer bonding material:
向环氧树脂中添加步骤四中制备的超支化聚氨酯改性杂环芳纶纤维环氧树脂固化剂，超声分散处理后高速搅拌混合均匀，即得到可常温固化的耐高温高粘高强高韧环氧树脂复合层间粘结材料。Add the hyperbranched polyurethane-modified heterocyclic aramid fiber epoxy resin curing agent prepared in step 4 to the epoxy resin, and stir and mix at high speed after ultrasonic dispersion treatment to obtain a high-temperature-resistant, high-viscosity, high-strength and high-toughness ring that can be cured at room temperature. Oxygen resin composite interlayer bonding material.
具体地，步骤一中制备得到的聚氨酯预聚体的结构式为：Specifically, the structural formula of the polyurethane prepolymer prepared in step 1 is:
步骤一中制备得到的超支化聚合物的结构式为：The structural formula of the hyperbranched polymer prepared in step 1 is:
步骤一中制备得到的脂肪族超支化聚氨酯的结构式为：The structural formula of the aliphatic hyperbranched polyurethane prepared in step 1 is:
本发明与现有技术相比，有益的技术效果是：Compared with the prior art, the present invention has the following beneficial technical effects:
(Ⅰ)本发明首次将超支化聚氨酯和多乙烯多胺同时用于杂环芳纶纤维改性，首次制得可固化环氧树脂的改性杂环芳纶纤维复合材料。(I) In the present invention, hyperbranched polyurethane and polyvinylpolyamine are used for the modification of heterocyclic aramid fibers for the first time, and the modified heterocyclic aramid fiber composite material of curable epoxy resin is prepared for the first time.
(Ⅱ)本发明采用的杂环芳纶纤维为一种起始单体为2,5-二氨基噻唑和对苯二甲酸，通过高温溶液聚合法合成的种五元含氮杂环聚芳酰胺，能溶解于二甲基亚砜和N，N-二甲基甲酰胺等有机溶剂，具有优异的热稳定性、溶解性能和力学性能。(II) The heterocyclic aramid fiber used in the present invention is a kind of five-membered nitrogen-containing heterocyclic polyaromatic amide synthesized by the high temperature solution polymerization method as the starting monomers are 2,5-diaminothiazole and terephthalic acid. , can be dissolved in dimethyl sulfoxide and N, N-dimethylformamide and other organic solvents, with excellent thermal stability, solubility and mechanical properties.
(Ⅲ)本发明采用20％的磷酸溶液(质量浓度)处理杂环芳纶纤维，能使纤维表面羟基—OH等含氧官能团数量增加，增加其活性。继续采用IP-DI溶液处理纤维，得表面含有高活泼性的羟基—OH、异氰酸根基—NCO和氨基—NH2纤维，为超支聚氨酯和多乙烯多胺的接支创造有利的条件。(III) The present invention uses 20% phosphoric acid solution (mass concentration) to treat the heterocyclic aramid fiber, which can increase the number of oxygen-containing functional groups such as hydroxyl-OH on the fiber surface and increase its activity. Continue to use IP-DI solution to treat the fibers, and the surface contains highly active hydroxyl-OH, isocyanato-NCO and amino-NH2 fibers, which create favorable conditions for the grafting of hyperbranched polyurethane and polyethylene polyamine.
(Ⅳ)本发明采用的超支化聚氨酯采用接枝共聚制得，在直链的聚氨酯预聚体分子链段上引入具有支化结构的端羟基超支化聚合物。超支化聚氨酯支化度高，具有椭球形结构，分子带有异氰酸根基、甲基、羟基等大量活性官能团，具有良好的流动性和溶解性，反应活性高，能顺利地接枝到经表面处理后的杂环芳纶纤维上；接枝超支化聚氨酯能明显改性杂环芳纶纤维表面活性，能有效提高其与环氧树脂间的粘接效果；且超支化聚氨酯具有优越的柔韧性和耐低温性能，用于环氧树脂增韧效果明显。(IV) The hyperbranched polyurethane used in the present invention is prepared by graft copolymerization, and a hydroxyl-terminated hyperbranched polymer with a branched structure is introduced into the molecular segment of the linear polyurethane prepolymer. Hyperbranched polyurethane has a high degree of branching, has an ellipsoid structure, and the molecule has a large number of active functional groups such as isocyanato groups, methyl groups, and hydroxyl groups. It has good fluidity and solubility, and has high reactivity. On the surface-treated heterocyclic aramid fiber; the grafted hyperbranched polyurethane can significantly modify the surface activity of the heterocyclic aramid fiber, which can effectively improve the bonding effect between it and the epoxy resin; and the hyperbranched polyurethane has superior flexibility. It has good toughness and low temperature resistance, and it has obvious toughening effect when used in epoxy resin.
(Ⅴ)本发明将多乙烯多胺接枝到杂环芳纶纤维以及超支聚氨酯表面并采用丁基缩水甘油醚对加成物进行封端，制得可固化环氧树脂的超支聚氨酯改性杂环芳纶纤维。(V) In the present invention, polyethylene polyamine is grafted onto the surface of heterocyclic aramid fiber and hyperbranched polyurethane, and butyl glycidyl ether is used to cap the adduct to obtain a hyperbranched polyurethane modified hybrid of curable epoxy resin. Cyclo-aramid fiber.
(Ⅵ)本发明制备的层间材料中经超支化聚氨酯改性杂环芳纶纤维能有效改善环氧树韧性低和耐冲击性差等缺点，且将多乙烯多胺接枝到改性杂环芳纶纤维上，使其在与环氧树脂进行物理交联的同时与环氧树脂产生化学键的结合环氧树脂固化，纤维与环氧树脂基体粘结效果优异，环氧树脂复合材料路用性能得到明显提升。(VI) In the interlayer material prepared by the present invention, the heterocyclic aramid fiber modified by hyperbranched polyurethane can effectively improve the shortcomings of epoxy resin, such as low toughness and poor impact resistance, and graft polyethylene polyamine to the modified heterocyclic ring. On the aramid fiber, it is physically cross-linked with the epoxy resin and at the same time produces a chemical bond with the epoxy resin. The epoxy resin is cured, and the bonding effect between the fiber and the epoxy resin matrix is excellent, and the road performance of the epoxy resin composite material significantly improved.
(Ⅶ)本发明采用超声波处理HBPU和杂环芳纶纤维制备表面接枝超支化聚氨酯的杂环芳纶纤维，以及采用超声波处理超支化聚氨酯改性杂环芳纶纤维环氧树脂固化剂和环氧树脂制备环氧树脂复合粘结材料，采用超声波处理纳米级杂环芳纶纤维使其具有在机械搅拌下无法达到的均匀分散和接触反应效果，使得超支聚氨酯和杂环芳纶纤维各项优异性能得到充分发挥的同时起到协同增强作用，制得性能优异的层间粘结材料。(VII) The present invention adopts ultrasonic treatment of HBPU and heterocyclic aramid fiber to prepare heterocyclic aramid fiber with surface grafted hyperbranched polyurethane, and adopts ultrasonic treatment to treat hyperbranched polyurethane modified heterocyclic aramid fiber epoxy resin curing agent and ring Oxygen resin is used to prepare epoxy resin composite bonding material, and nano-heterocyclic aramid fiber is treated with ultrasonic wave to make it have uniform dispersion and contact reaction effects that cannot be achieved under mechanical stirring, which makes hyperbranched polyurethane and heterocyclic aramid fiber excellent in various aspects. While the performance is fully exerted, it plays a synergistic strengthening role, and an interlayer bonding material with excellent performance is obtained.
具体实施方式Detailed ways
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, but not to limit the present invention.
实施例1：Example 1:
本实施例给出一种耐高温高粘高强高韧层间粘结材料，以重量份数计，由以下原料制成：聚四氢呋喃醚二醇(PTMG)15份、异佛尔酮二异氰酸酯(IP-DI)5份、丁二酸酐5份、二乙醇胺5份、三羟甲基丙烷4份、杂环芳纶纤维35份、环氧树脂100份、三乙烯四胺12份。The present embodiment provides a high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material, which is made of the following raw materials in parts by weight: 15 parts of polytetrahydrofuran ether glycol (PTMG), isophorone diisocyanate ( IP-DI) 5 parts, succinic anhydride 5 parts, diethanolamine 5 parts, trimethylolpropane 4 parts, heterocyclic aramid fiber 35 parts, epoxy resin 100 parts, triethylene tetramine 12 parts.
本实施例中的杂环芳纶纤维是五元含氮杂环聚芳酰胺，具体的结构式为：The heterocyclic aramid fiber in this embodiment is a five-membered nitrogen-containing heterocyclic polyaramid, and the specific structural formula is:
其中：n取值范围为100～1000。所述的杂环芳纶纤维为一种起始单体为2，5-二氨基噻唑和对苯二甲酸，通过高温溶液聚合法合成的一种五元含氮杂环聚芳酰胺，能溶解于二甲基亚砜和N，N-二甲基甲酰胺等有机溶剂，熔点大于310℃。Among them: n is in the range of 100 to 1000. Said heterocyclic aramid fiber is a kind of five-membered nitrogen-containing heterocyclic polyaromatic amide synthesized by high temperature solution polymerization with the starting monomers of 2,5-diaminothiazole and terephthalic acid, which can dissolve In organic solvents such as dimethyl sulfoxide and N,N-dimethylformamide, the melting point is higher than 310℃.
本实施例中的环氧树脂为双酚A型环氧树脂E-44，双酚A型环氧树脂E-44的环氧值为0.41～0.47eq/100g、环氧当量为212～244g/eq。The epoxy resin in this embodiment is bisphenol A type epoxy resin E-44, the epoxy value of bisphenol A type epoxy resin E-44 is 0.41～0.47eq/100g, and the epoxy equivalent weight is 212～244g/ eq.
本实施例中，聚四氢呋喃醚二醇的分子量Mn＝1000，聚合度n＝13.6。In this embodiment, the molecular weight of the polytetrahydrofuran ether diol is Mn=1000, and the degree of polymerization is n=13.6.
本实施例的耐高温高粘高强高韧层间粘结材料的制备方法，采用所述的耐高温高粘高强高韧层间粘结材料的原料，该方法包括以下步骤：The preparation method of the high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material of the present embodiment adopts the raw material of the high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material, and the method includes the following steps:
步骤一：制备脂肪族超支化聚氨酯：Step 1: Preparation of Aliphatic Hyperbranched Polyurethane:
以N，N-二甲基甲酰胺(DMF)作为溶剂，加入干燥后的聚四氢呋喃醚二醇、采用二月桂酸二丁基锡为催化剂，滴加异佛尔酮二异氰酸酯，在氮气气氛中，75℃下反应1.5h，得到—NCO封端的聚氨酯预聚体(PPU)；Using N,N-dimethylformamide (DMF) as a solvent, adding dried polytetrahydrofuran ether diol, using dibutyltin dilaurate as a catalyst, adding isophorone diisocyanate dropwise, in a nitrogen atmosphere, 75 React at ℃ for 1.5 h to obtain -NCO-terminated polyurethane prepolymer (PPU);
以甲醇作溶剂，冰水浴下加入丁二酸酐和二乙醇胺，氮气气氛中反应6h，干燥得4-(双(2-羟乙基)亚胺)-4-氧代丁酸(AB2)单体；继续将三羟甲基丙烷和上述4-(双(2-羟乙基)亚胺)-4-氧代丁酸(AB2)单体加入到反应釜中，以甲苯磺酸作催化剂，甲苯为带水剂，在120℃下酯化反应8h至无水生成，得到淡黄色黏稠液体即为超支化聚合物(HPAE)；Using methanol as a solvent, add succinic anhydride and diethanolamine in an ice-water bath, react in a nitrogen atmosphere for 6 h, and dry to obtain 4-(bis(2-hydroxyethyl)imine)-4-oxobutyric acid (AB2) monomer Continue to join trimethylolpropane and above-mentioned 4-(two (2-hydroxyethyl) imine)-4-oxobutyric acid (AB2) monomer in the reactor, make catalyzer with toluenesulfonic acid, toluene As a water-carrying agent, the esterification reaction is carried out at 120 ° C for 8 hours until anhydrous is formed, and a light yellow viscous liquid is obtained, which is a hyperbranched polymer (HPAE);
在上述制备好的聚氨酯预聚体(PPU)中加入制备的超支化聚合物HPAE，在氮气气氛中，75℃下反应4.5h，得到无色粘稠液体即为脂肪族超支化聚氨酯(HBPU)；Add the prepared hyperbranched polymer HPAE to the above prepared polyurethane prepolymer (PPU), and react in a nitrogen atmosphere at 75 ° C for 4.5 hours to obtain a colorless viscous liquid, which is aliphatic hyperbranched polyurethane (HBPU) ;
具体的，步骤一中制备得到的聚氨酯预聚体的结构式为：Specifically, the structural formula of the polyurethane prepolymer prepared in step 1 is:
步骤一中制备得到的超支化聚合物的结构式为：The structural formula of the hyperbranched polymer prepared in step 1 is:
步骤一中制备得到的脂肪族超支化聚氨酯的结构式为：The structural formula of the aliphatic hyperbranched polyurethane prepared in step 1 is:
其中，聚氨酯预聚体(PPU)中加入超支化聚合物HPAE，反应过程如下：Wherein, the hyperbranched polymer HPAE is added in the polyurethane prepolymer (PPU), and the reaction process is as follows:
步骤二：杂环芳纶纤维表面处理：Step 2: Heterocyclic aramid fiber surface treatment:
将400目杂环芳纶纤维用丙酮超声清洗2h后烘干，再在质量浓度为20％、温度为40℃的磷酸溶液中浸泡，浸泡后在80℃下真空干燥12h，再加入到异佛尔酮二异氰酸酯的溶液中反应，用去离子清洗至中性并干燥后得到表面含有高活泼性的羟基—OH、异氰酸根基—NCO和氨基—NH2的表面处理的杂环芳纶纤维；The 400-mesh heterocyclic aramid fiber was ultrasonically cleaned with acetone for 2 hours, then dried, and then soaked in a phosphoric acid solution with a mass concentration of 20% and a temperature of 40 ° C. After soaking, it was vacuum-dried at 80 ° C for 12 hours, and then added to Yifo Reaction in the solution of ketone diisocyanate, cleaning with deionization to neutrality and drying to obtain surface-treated heterocyclic aramid fibers containing highly active hydroxyl-OH, isocyanato-NCO and amino-NH2 on the surface;
步骤三：杂环芳纶纤维表面接枝处理：Step 3: Surface Grafting Treatment of Heterocyclic Aramid Fiber:
将步骤一制备的脂肪族超支化聚氨酯(HBPU)加入反应釜中，用N，N-二甲基甲酰胺作稀释剂，加入上述步骤二经过表面处理的杂环芳纶纤维，80～90℃下经超声波处理后，在高速剪切的条件下反应5小时得到表面接枝超支化聚氨酯的杂环芳纶纤维，分离、提纯、干燥得超支化聚氨酯改性杂环芳纶纤维；Add the aliphatic hyperbranched polyurethane (HBPU) prepared in step 1 into the reaction kettle, use N,N-dimethylformamide as a diluent, add the surface-treated heterocyclic aramid fiber in the above step 2, 80～90℃ After ultrasonic treatment, react under high-speed shearing conditions for 5 hours to obtain the surface-grafted heterocyclic aramid fiber of hyperbranched polyurethane, and separate, purify and dry to obtain the hyperbranched polyurethane modified heterocyclic aramid fiber;
步骤四：环氧树脂固化剂的制备：Step 4: Preparation of epoxy resin curing agent:
将步骤三中得到的超支化聚氨酯改性杂环芳纶纤维和环氧树脂溶于丙二醇甲醚后，加入反应釜中与表面活性剂在70℃反应3.5h，再加入多乙烯多胺进行加成反应，添加丁基缩水甘油醚对加成物进行封端，反应结束后降温至50℃加入冰醋酸调节亲水亲油平衡，在减压条件下蒸馏出溶剂，即得超支化聚氨酯改性杂环芳纶纤维环氧树脂固化剂；After dissolving the hyperbranched polyurethane-modified heterocyclic aramid fiber and epoxy resin obtained in step 3 in propylene glycol methyl ether, it was added to the reaction kettle and reacted with the surfactant at 70 ° C for 3.5 hours, and then polyethylene polyamine was added. After the reaction is completed, butyl glycidyl ether is added to cap the adduct. After the reaction, the temperature is lowered to 50 °C and glacial acetic acid is added to adjust the hydrophilic-lipophilic balance. The solvent is distilled off under reduced pressure to obtain hyperbranched polyurethane modification. Heterocyclic aramid fiber epoxy resin curing agent;
步骤五：制备层间粘结材料：Step 5: Preparation of interlayer bonding material:
向环氧树脂中添加步骤四中制备的超支化聚氨酯改性杂环芳纶纤维环氧树脂固化剂，超声分散处理后高速搅拌混合均匀，即得到可常温固化的耐高温高粘高强高韧环氧树脂复合层间粘结材料。Add the hyperbranched polyurethane-modified heterocyclic aramid fiber epoxy resin curing agent prepared in step 4 to the epoxy resin, and stir and mix at high speed after ultrasonic dispersion treatment to obtain a high-temperature-resistant, high-viscosity, high-strength and high-toughness ring that can be cured at room temperature. Oxygen resin composite interlayer bonding material.
实施例2：Example 2:
本实施例给出一种耐高温高粘高强高韧层间粘结材料，以重量份数计，由以下原材料制成PTMG18份、IP-DI7份、丁二酸酐7份、二乙醇胺8份、三羟甲基丙烷5份、杂环芳纶纤维35份、环氧树脂100份、三乙烯四胺12份。This example provides a high-temperature-resistant, high-viscosity, high-strength, and high-toughness interlayer bonding material. In parts by weight, it is made from the following raw materials: 18 parts of PTMG, 7 parts of IP-DI, 7 parts of succinic anhydride, 8 parts of diethanolamine, 5 parts of trimethylolpropane, 35 parts of heterocyclic aramid fiber, 100 parts of epoxy resin, and 12 parts of triethylenetetramine.
本实施例中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this example are the same as those in Example 1.
本实施例的耐高温高粘高强高韧层间粘结材料的制备方法与实施例1相同。The preparation method of the high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material of this embodiment is the same as that of embodiment 1.
实施例3：Example 3:
本实施例给出一种耐高温高粘高强高韧层间粘结材料，以重量份数计，由以下原材料制成：PTMG20份、IP-DI10份、丁二酸酐10份、二乙醇胺10份、三羟甲基丙烷8份、杂环芳纶纤维35份、环氧树脂100份、三乙烯四胺12份。This example provides an interlayer bonding material with high temperature resistance, high viscosity, high strength and high toughness, which is made of the following raw materials in parts by weight: 20 parts of PTMG, 10 parts of IP-DI, 10 parts of succinic anhydride, and 10 parts of diethanolamine , 8 parts of trimethylolpropane, 35 parts of heterocyclic aramid fiber, 100 parts of epoxy resin, and 12 parts of triethylenetetramine.
本实施例中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this example are the same as those in Example 1.
本实施例的耐高温高粘高强高韧层间粘结材料的制备方法与实施例1相同。The preparation method of the high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material of this embodiment is the same as that of embodiment 1.
实施例4：Example 4:
本实施例给出一种耐高温高粘高强高韧层间粘结材料，以重量份数计，由以下原材料制成：PTMG 18份、IP-DI 7份、丁二酸酐7份、二乙醇胺8份、三羟甲基丙烷5份、杂环芳纶纤维30份、环氧树脂100份、三乙烯四胺12份。This example provides an interlayer bonding material with high temperature resistance, high viscosity, high strength and high toughness, which is made of the following raw materials in parts by weight: 18 parts of PTMG, 7 parts of IP-DI, 7 parts of succinic anhydride, and diethanolamine 8 parts, 5 parts of trimethylolpropane, 30 parts of heterocyclic aramid fibers, 100 parts of epoxy resin, and 12 parts of triethylenetetramine.
本实施例中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this example are the same as those in Example 1.
本实施例的耐高温高粘高强高韧层间粘结材料的制备方法与实施例1相同。The preparation method of the high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material of this embodiment is the same as that of embodiment 1.
实施例5：Example 5:
本实施例给出一种耐高温高粘高强高韧层间粘结材料，以重量份数计，由以下原材料制成：PTMG 18份、IP-DI 7份、丁二酸酐7份、二乙醇胺8份、三羟甲基丙烷5份、杂环芳纶纤维40份、环氧树脂100份、三乙烯四胺12份。This example provides an interlayer bonding material with high temperature resistance, high viscosity, high strength and high toughness, which is made of the following raw materials in parts by weight: 18 parts of PTMG, 7 parts of IP-DI, 7 parts of succinic anhydride, and diethanolamine 8 parts, 5 parts of trimethylolpropane, 40 parts of heterocyclic aramid fibers, 100 parts of epoxy resin, and 12 parts of triethylenetetramine.
本实施例中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this example are the same as those in Example 1.
本实施例的耐高温高粘高强高韧层间粘结材料的制备方法与实施例1相同。The preparation method of the high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material of this embodiment is the same as that of embodiment 1.
实施例6：Example 6:
本实施例给出一种耐高温高粘高强高韧层间粘结材料，以重量份数计，由以下原材料制成：PTMG 18份、IP-DI 7份、丁二酸酐7份、二乙醇胺8份、三羟甲基丙烷5份、杂环芳纶纤维35份、环氧树脂100份、三乙烯四胺10份。This example provides an interlayer bonding material with high temperature resistance, high viscosity, high strength and high toughness, which is made of the following raw materials in parts by weight: 18 parts of PTMG, 7 parts of IP-DI, 7 parts of succinic anhydride, and diethanolamine 8 parts, 5 parts of trimethylolpropane, 35 parts of heterocyclic aramid fibers, 100 parts of epoxy resin, and 10 parts of triethylenetetramine.
本实施例中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this example are the same as those in Example 1.
本实施例的耐高温高粘高强高韧层间粘结材料的制备方法与实施例1相同。The preparation method of the high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material of this embodiment is the same as that of embodiment 1.
实施例7：Example 7:
本实施例给出一种耐高温高粘高强高韧层间粘结材料，以重量份数计，由以下原材料制成：PTMG 18份、IP-DI 7份、丁二酸酐7份、二乙醇胺8份、三羟甲基丙烷5份、杂环芳纶纤维35份、环氧树脂100份、三乙烯四胺15份。This example provides an interlayer bonding material with high temperature resistance, high viscosity, high strength and high toughness, which is made of the following raw materials in parts by weight: 18 parts of PTMG, 7 parts of IP-DI, 7 parts of succinic anhydride, and diethanolamine 8 parts, 5 parts of trimethylolpropane, 35 parts of heterocyclic aramid fiber, 100 parts of epoxy resin, and 15 parts of triethylenetetramine.
本实施例中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this example are the same as those in Example 1.
本实施例的耐高温高粘高强高韧层间粘结材料的制备方法与实施例1相同。The preparation method of the high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material of this embodiment is the same as that of embodiment 1.
实施例8：Example 8:
本实施例给出一种耐高温高粘高强高韧层间粘结材料，以重量份数计，由以下原材料制成：PTMG 15份、IP-DI 5份、丁二酸酐5份、二乙醇胺5份、三羟甲基丙烷5份、杂环芳纶纤维30份、环氧树脂100份、三乙烯四胺10份。The present embodiment provides an interlayer bonding material with high temperature resistance, high viscosity, high strength and high toughness, which is made of the following raw materials in parts by weight: 15 parts of PTMG, 5 parts of IP-DI, 5 parts of succinic anhydride, and diethanolamine 5 parts, 5 parts of trimethylolpropane, 30 parts of heterocyclic aramid fiber, 100 parts of epoxy resin, and 10 parts of triethylenetetramine.
本实施例中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this example are the same as those in Example 1.
本实施例的耐高温高粘高强高韧层间粘结材料的制备方法与实施例1相同。The preparation method of the high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material of this embodiment is the same as that of embodiment 1.
实施例9：Example 9:
本实施例给出一种耐高温高粘高强高韧层间粘结材料，以重量份数计，由以下原材料制成：PTMG 20份、IP-DI 10份、丁二酸酐10份、二乙醇胺10份、三羟甲基丙烷8份、杂环芳纶纤维40份、环氧树脂100份、三乙烯四胺15份。This example provides an interlayer bonding material with high temperature resistance, high viscosity, high strength and high toughness, which is made of the following raw materials in parts by weight: 20 parts of PTMG, 10 parts of IP-DI, 10 parts of succinic anhydride, and diethanolamine 10 parts, 8 parts of trimethylolpropane, 40 parts of heterocyclic aramid fibers, 100 parts of epoxy resin, and 15 parts of triethylenetetramine.
本实施例中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this example are the same as those in Example 1.
本实施例的耐高温高粘高强高韧层间粘结材料的制备方法与实施例1相同。The preparation method of the high-temperature-resistant, high-viscosity, high-strength and high-toughness interlayer bonding material of this embodiment is the same as that of embodiment 1.
对比例1：Comparative Example 1:
本对比例给出一种层间粘结材料，本对比例与实施例2不同之处在于，环氧树脂未进行改性处理。This comparative example provides an interlayer bonding material. The difference between this comparative example and Example 2 is that the epoxy resin is not modified.
本对比例以重量份数计，由以下原材料制成：环氧树脂双酚A型环氧树脂E-44 100份、三乙烯四胺12份。In parts by weight, this comparative example is made from the following raw materials: 100 parts of epoxy resin bisphenol A type epoxy resin E-44, and 12 parts of triethylenetetramine.
本对比例中所用环氧树脂和三乙烯四胺与实施例1相同。The epoxy resin and triethylenetetramine used in this comparative example are the same as in Example 1.
本对比例的层间粘结材料的制备方法按照如下步骤进行：The preparation method of the interlayer bonding material of this comparative example is carried out according to the following steps:
向环氧树脂中添加三乙烯四胺，超声分散处理后高速搅拌混合均匀即得到一种层间粘结材料。Triethylenetetramine is added to the epoxy resin, and after ultrasonic dispersion treatment, high-speed stirring and mixing are uniform to obtain an interlayer bonding material.
对比例2：Comparative Example 2:
本对比例给出一种层间粘结材料，本对比例与实施例2不同之处在于，仅采用超支化聚氨酯对环氧树脂进行改性。This comparative example provides an interlayer bonding material. The difference between this comparative example and Example 2 is that only hyperbranched polyurethane is used to modify the epoxy resin.
本对比例以重量份数计，由以下原材料制成：PTMG 18份、IP-DI 7份、丁二酸酐7份、二乙醇胺8份、三羟甲基丙烷5份、环氧树脂100份、三乙烯四胺12份。This comparative example is made of the following raw materials in parts by weight: 18 parts of PTMG, 7 parts of IP-DI, 7 parts of succinic anhydride, 8 parts of diethanolamine, 5 parts of trimethylolpropane, 100 parts of epoxy resin, 12 parts of triethylenetetramine.
本对比中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this comparison are the same as those in Example 1.
本对比例的层间粘结材料的制备方法按照如下步骤进行：The preparation method of the interlayer bonding material of this comparative example is carried out according to the following steps:
步骤一，按照实施例1的脂肪族超支聚氨酯的制备方法制备超支聚氨酯。In step 1, hyperbranched polyurethane is prepared according to the preparation method of aliphatic hyperbranched polyurethane in Example 1.
步骤二，将环氧树脂、三乙烯四胺和超支化聚氨酯在超声分散处理后高速搅拌混合均匀即得到一种层间粘结材料。In step 2, the epoxy resin, triethylenetetramine and hyperbranched polyurethane are uniformly mixed at a high speed after ultrasonic dispersion treatment to obtain an interlayer bonding material.
对比例3：Comparative Example 3:
本对比例给出一种层间粘结材料，本对比例与实施例2不同之处在于，仅采用杂环芳纶纤维对环氧树脂进行改性。This comparative example provides an interlayer bonding material. The difference between this comparative example and Example 2 is that only heterocyclic aramid fibers are used to modify the epoxy resin.
本对比例以重量份数计，由以下原材料制成：杂环芳纶纤维35份、环氧树脂100份、三乙烯四胺12份。In parts by weight, this comparative example is made from the following raw materials: 35 parts of heterocyclic aramid fibers, 100 parts of epoxy resin, and 12 parts of triethylenetetramine.
本对比例中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this comparative example are the same as those in Example 1.
本对比例的层间材料的制备方法按照如下步骤进行：The preparation method of the interlayer material of this comparative example is carried out according to the following steps:
步骤一，杂环芳纶纤维表面处理。将400目杂环芳纶纤维用丙酮超声清洗2h后，为增加纤维表面含氧官能团含量将其烘干后加入20％的磷酸溶液(质量浓度)，40℃下浸泡一定时间后取出，在80℃下真空干燥12h，加入IP-DI溶液中反应一定时间取出，用去离子水清洗至中性并干燥，得表面含有高活泼性的羟基—OH、异氰酸根基—NCO和氨基—NH2纤维。Step 1, surface treatment of heterocyclic aramid fibers. The 400-mesh heterocyclic aramid fiber was ultrasonically cleaned with acetone for 2 h, dried and added with 20% phosphoric acid solution (mass concentration) in order to increase the oxygen-containing functional group content on the surface of the fiber, soaked at 40 °C for a certain period of time, and then taken out, and placed at 80 °C. It was vacuum-dried at ℃ for 12 h, added to IP-DI solution and reacted for a certain period of time and taken out, washed with deionized water until neutral and dried to obtain fibers containing highly reactive hydroxyl-OH, isocyanato-NCO and amino-NH2 fibers on the surface. .
步骤二，环氧树脂固化剂制备。将上述杂环芳纶纤维和环氧树脂双酚A型环氧树脂E-44溶于丙二醇甲醚加入反应釜中与表面活性剂在70℃反应3.5h，再加入多乙烯多胺进行加成反应，添加丁基缩水甘油醚对加成物进行封端，反应结束后降温至50℃加入冰醋酸调节亲水亲油平衡，在减压条件下蒸馏出溶剂，即得杂环芳纶纤维改性环氧树脂固化剂。Step 2, preparation of epoxy resin curing agent. The above heterocyclic aramid fiber and epoxy resin bisphenol A epoxy resin E-44 were dissolved in propylene glycol methyl ether, added to the reaction kettle and reacted with surfactant at 70 ℃ for 3.5h, and then polyethylene polyamine was added for addition After the reaction, butyl glycidyl ether is added to cap the adduct, and after the reaction is completed, the temperature is lowered to 50 ° C and glacial acetic acid is added to adjust the hydrophilic-lipophilic balance, and the solvent is distilled off under reduced pressure to obtain the modified heterocyclic aramid fiber. Epoxy resin curing agent.
步骤三，制备层间粘结材料。向环氧树脂中添加上述杂环芳纶纤维改性环氧树脂固化剂，超声分散处理后高速搅拌混合均匀，即得到一种层间粘结材料。Step 3, prepare the interlayer bonding material. The above-mentioned heterocyclic aramid fiber modified epoxy resin curing agent is added to the epoxy resin, and after ultrasonic dispersion treatment, high-speed stirring and mixing are uniform, so as to obtain an interlayer bonding material.
对比例4：Comparative Example 4:
本对比例给出一种层间粘结材料，本对比例与实施例2不同之处在于，仅将制备好的超支聚氨酯、经表面处理后的杂环芳纶纤维和三乙烯四胺直接添加到环氧树脂中制备环氧树脂复合材料。This comparative example provides an interlayer bonding material. The difference between this comparative example and Example 2 is that only the prepared hyperbranched polyurethane, the surface-treated heterocyclic aramid fiber and triethylenetetramine are directly added Epoxy resin composites are prepared into epoxy resins.
本对比例以重量份数计，由以下原材料制成：PTMG 18份、IP-DI 7份、丁二酸酐7份、二乙醇胺8份、三羟甲基丙烷5份、杂环芳纶纤维35份、环氧树脂100份、三乙烯四胺12份。This comparative example is made of the following raw materials in parts by weight: 18 parts of PTMG, 7 parts of IP-DI, 7 parts of succinic anhydride, 8 parts of diethanolamine, 5 parts of trimethylolpropane, 35 parts of heterocyclic aramid fibers parts, 100 parts of epoxy resin, and 12 parts of triethylenetetramine.
本对比例中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this comparative example are the same as those in Example 1.
本对比例的层间材料的制备方法按照如下步骤进行：The preparation method of the interlayer material of this comparative example is carried out according to the following steps:
步骤一，分别按照实施例1步骤一和步骤二的方法进行超支聚氨酯的制备和杂环芳纶纤维表面处理。In step 1, the preparation of hyperbranched polyurethane and the surface treatment of heterocyclic aramid fibers are carried out respectively according to the methods of step 1 and step 2 of Example 1.
步骤二，制备层间粘结材料。向环氧树脂中添加超支聚氨酯和经表面处理后的杂环芳纶纤维，超声分散处理后，高速剪混合均匀，继续添加三乙烯四胺，超声分散后高速搅拌混合均匀，即得到一种环氧树脂复合层间粘结材料。The second step is to prepare the interlayer bonding material. Add hyperbranched polyurethane and surface-treated heterocyclic aramid fiber to the epoxy resin, after ultrasonic dispersion treatment, mix uniformly at high speed, continue to add triethylenetetramine, and mix uniformly at high speed after ultrasonic dispersion, that is, a ring is obtained. Oxygen resin composite interlayer bonding material.
对比例5：Comparative Example 5:
本对比例给出一种层间粘结材料，本对比例与实施例2不同之处在于，仅将接枝超支聚氨酯的杂环芳纶纤维和三乙烯四胺直接添加到环氧树脂中制备环氧树脂复合材料。This comparative example provides an interlayer bonding material. The difference between this comparative example and Example 2 is that only the heterocyclic aramid fiber and triethylenetetramine grafted with hyperbranched polyurethane are directly added to the epoxy resin to prepare epoxy resin composite.
本对比例以重量份数计，由以下原材料制成：PTMG 18份、IP-DI 7份、丁二酸酐7份、二乙醇胺8份、三羟甲基丙烷5份、杂环芳纶纤维35份、环氧树脂100份、三乙烯四胺12份。This comparative example is made of the following raw materials in parts by weight: 18 parts of PTMG, 7 parts of IP-DI, 7 parts of succinic anhydride, 8 parts of diethanolamine, 5 parts of trimethylolpropane, 35 parts of heterocyclic aramid fibers parts, 100 parts of epoxy resin, and 12 parts of triethylenetetramine.
本对比例中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this comparative example are the same as those in Example 1.
本对比例的层间材料的制备方法按照如下步骤进行：The preparation method of the interlayer material of this comparative example is carried out according to the following steps:
步骤一，分别按照实施例1中步骤一和步骤二的方法进行超支聚氨酯的制备和杂环芳纶纤维表面处理。In step 1, the preparation of hyperbranched polyurethane and the surface treatment of heterocyclic aramid fibers are carried out respectively according to the methods of step 1 and step 2 in Example 1.
步骤二，杂环芳纶纤维表面接枝处理。将所制备的HBPU加入反应釜中，用N，N-二甲基甲酰胺作稀释剂，加入上述经过表面处理的杂环芳纶纤维，升温至80～90℃经超声波处理后，在高速剪切和催化剂的条件下反应5小时得到表面接枝超支化聚氨酯的杂环芳纶纤维，分离、提纯、干燥得超支化聚氨酯改性杂环芳纶纤维。Step 2, grafting the surface of the heterocyclic aramid fiber. The prepared HBPU was added to the reaction kettle, and N,N-dimethylformamide was used as a diluent, and the above-mentioned surface-treated heterocyclic aramid fibers were added, and the temperature was raised to 80-90° C. After ultrasonic treatment, it was subjected to high-speed shearing. The heterocyclic aramid fiber with surface grafted hyperbranched polyurethane is obtained by reacting under the condition of cutting and catalyst for 5 hours, and separating, purifying and drying to obtain the hyperbranched polyurethane modified heterocyclic aramid fiber.
步骤三，制备层间粘结材料。向环氧树脂中添加上述超支化聚氨酯改性杂环芳纶纤维，超声波处理后，高速剪切混合均匀，继续添加三乙烯四胺，超声分散处理后高速搅拌混合均匀，即得到一种环氧树脂复合层间粘结材料。Step 3, prepare the interlayer bonding material. The above hyperbranched polyurethane modified heterocyclic aramid fiber is added to the epoxy resin, and after ultrasonic treatment, high-speed shearing and mixing are uniform, and triethylene tetramine is continued to be added, and after ultrasonic dispersion treatment, high-speed stirring and mixing are uniform to obtain an epoxy resin. Resin composite interlayer bonding material.
对比例6：Comparative Example 6:
本对比例给出一种层间粘结材料，本对比例与实施例2不同之处在于，采用等质量的超支化聚氨酯替代杂环芳纶纤维对环氧树脂进行改性，本对比例以重量份数计，由以下原材料制成：PTMG 35份、IP-DI 14份、丁二酸酐14份、二乙醇胺16份、三羟甲基丙烷10份、环氧树脂100份、三乙烯四胺12份。This comparative example provides an interlayer bonding material. The difference between this comparative example and Example 2 is that the epoxy resin is modified by using the same quality of hyperbranched polyurethane instead of the heterocyclic aramid fiber. In parts by weight, it is made from the following raw materials: 35 parts of PTMG, 14 parts of IP-DI, 14 parts of succinic anhydride, 16 parts of diethanolamine, 10 parts of trimethylolpropane, 100 parts of epoxy resin, and triethylene tetramine 12 servings.
本对比中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this comparison are the same as those in Example 1.
本对比例的层间粘结材料的制备方法按照如下步骤进行：The preparation method of the interlayer bonding material of this comparative example is carried out according to the following steps:
步骤一，按照实施例1的脂肪族超支聚氨酯的制备方法制备超支聚氨酯。In step 1, hyperbranched polyurethane is prepared according to the preparation method of aliphatic hyperbranched polyurethane in Example 1.
步骤二，将环氧树脂、三乙烯四胺和超支化聚氨酯在超声分散处理后高速搅拌混合均匀即得到一种层间粘结材料。In step 2, the epoxy resin, triethylenetetramine and hyperbranched polyurethane are uniformly mixed at a high speed after ultrasonic dispersion treatment to obtain an interlayer bonding material.
对比例7：Comparative Example 7:
本对比例给出一种层间粘结材料，本对比例与实施例2不同之处在于，采用等质量的杂环芳纶纤维替代超支聚氨酯对环氧树脂进行改性。This comparative example provides an interlayer bonding material. The difference between this comparative example and Example 2 is that the epoxy resin is modified by using the same quality heterocyclic aramid fiber instead of hyperbranched polyurethane.
本对比例以重量份数计，由以下原材料制成：杂环芳纶纤维75份、环氧树脂100份、三乙烯四胺12份。In parts by weight, this comparative example is made from the following raw materials: 75 parts of heterocyclic aramid fibers, 100 parts of epoxy resin, and 12 parts of triethylenetetramine.
本对比例中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this comparative example are the same as those in Example 1.
本对比例的层间材料的制备方法按照如下步骤进行：The preparation method of the interlayer material of this comparative example is carried out according to the following steps:
步骤一，杂环芳纶纤维表面处理。将400目杂环芳纶纤维用丙酮超声清洗2h后，为增加纤维表面含氧官能团含量将其烘干后加入20％的磷酸溶液(质量浓度)，40℃下浸泡一定时间后取出，在80℃下真空干燥12h，加入IP-DI溶液中反应一定时间取出，用去离子水清洗至中性并干燥，得表面含有高活泼性的羟基—OH、异氰酸根基—NCO和氨基—NH2纤维。Step 1, surface treatment of heterocyclic aramid fibers. The 400-mesh heterocyclic aramid fiber was ultrasonically cleaned with acetone for 2 h, dried and added with 20% phosphoric acid solution (mass concentration) in order to increase the oxygen-containing functional group content on the surface of the fiber, soaked at 40 °C for a certain period of time, and then taken out, and placed at 80 °C. It was vacuum-dried at ℃ for 12 h, added to IP-DI solution and reacted for a certain period of time and taken out, washed with deionized water until neutral and dried to obtain fibers containing highly reactive hydroxyl-OH, isocyanato-NCO and amino-NH2 fibers on the surface. .
步骤二，环氧树脂固化剂制备。将上述杂环芳纶纤维和环氧树脂双酚A型环氧树脂E-44溶于丙二醇甲醚加入反应釜中与表面活性剂在70℃反应3.5h，再加入多乙烯多胺进行加成反应，添加丁基缩水甘油醚对加成物进行封端，反应结束后降温至50℃加入冰醋酸调节亲水亲油平衡，在减压条件下蒸馏出溶剂，即得杂环芳纶纤维改性环氧树脂固化剂。Step 2, preparation of epoxy resin curing agent. The above heterocyclic aramid fiber and epoxy resin bisphenol A epoxy resin E-44 were dissolved in propylene glycol methyl ether, added to the reaction kettle and reacted with surfactant at 70 ℃ for 3.5h, and then polyethylene polyamine was added for addition After the reaction, butyl glycidyl ether is added to cap the adduct, and after the reaction is completed, the temperature is lowered to 50 ° C and glacial acetic acid is added to adjust the hydrophilic-lipophilic balance, and the solvent is distilled off under reduced pressure to obtain the modified heterocyclic aramid fiber. Epoxy resin curing agent.
步骤三，制备层间粘结材料。向环氧树脂中添加上述杂环芳纶纤维改性环氧树脂固化剂，超声分散处理后高速搅拌混合均匀，即得到一种层间粘结材料。Step 3, prepare the interlayer bonding material. The above-mentioned heterocyclic aramid fiber modified epoxy resin curing agent is added to the epoxy resin, and after ultrasonic dispersion treatment, high-speed stirring and mixing are uniform, so as to obtain an interlayer bonding material.
对比例8：Comparative Example 8:
本对比例给出一种层间粘结材料，本对比例与实施例7不同之处在于，仅采用高速剪切、机械搅拌的方法制备超支化聚氨酯改性杂环芳纶纤维环氧树脂固化剂以及环氧树脂复合材料，制备过程中未使用超声波处理。This comparative example provides an interlayer bonding material. The difference between this comparative example and Example 7 is that only the method of high-speed shearing and mechanical stirring is used to prepare hyperbranched polyurethane modified heterocyclic aramid fiber epoxy resin curing agent and epoxy resin composite, and ultrasonic treatment was not used in the preparation process.
本对比例以重量份数计，由以下原材料制成：PTMG 18份、IP-DI 7份、丁二酸酐7份、二乙醇胺8份、三羟甲基丙烷5份、杂环芳纶纤维35份、环氧树脂100份、三乙烯四胺15份。This comparative example is made of the following raw materials in parts by weight: 18 parts of PTMG, 7 parts of IP-DI, 7 parts of succinic anhydride, 8 parts of diethanolamine, 5 parts of trimethylolpropane, 35 parts of heterocyclic aramid fibers parts, 100 parts of epoxy resin, and 15 parts of triethylenetetramine.
本对比例中原料的选择和规格与实施例1相同。The selection and specification of raw materials in this comparative example are the same as those in Example 1.
本对比例的层间材料的制备方法按照如下步骤进行：The preparation method of the interlayer material of this comparative example is carried out according to the following steps:
步骤一，分别按照实施例1中步骤一和步骤二的方法进行超支聚氨酯的制备和杂环芳纶纤维表面处理。In step 1, the preparation of hyperbranched polyurethane and the surface treatment of heterocyclic aramid fibers are carried out respectively according to the methods of step 1 and step 2 in Example 1.
步骤二，杂环芳纶纤维表面接枝处理和环氧树脂固化剂制备。将所制备的HBPU加入反应釜中，用N，N-二甲基甲酰胺作稀释剂，加入上述经过表面处理的杂环芳纶纤维，升温至80～90℃，在高速剪切和催化剂的条件下反应5小时得到表面接枝超支化聚氨酯的杂环芳纶纤维，分离、提纯、干燥得超支化聚氨酯改性杂环芳纶纤维。将上述制备的改性杂环芳纶纤维和环氧树脂双酚A型环氧树脂E-44溶于丙二醇甲醚，加入反应釜中与表面活性剂在70℃反应3.5h,再加入多乙烯多胺进行加成反应,添加丁基缩水甘油醚对加成物进行封端，反应结束后降温至50℃加入冰醋酸调节亲水亲油平衡，在减压条件下蒸馏出溶剂，即得超支化聚氨酯改性杂环芳纶纤维环氧树脂固化剂。Step 2, the surface grafting treatment of the heterocyclic aramid fiber and the preparation of the epoxy resin curing agent. The prepared HBPU was added to the reaction kettle, and N,N-dimethylformamide was used as a diluent, and the above-mentioned surface-treated heterocyclic aramid fibers were added, and the temperature was raised to 80-90°C. The heterocyclic aramid fiber with the surface grafted hyperbranched polyurethane is obtained by reacting under the conditions for 5 hours, and the hyperbranched polyurethane modified heterocyclic aramid fiber is obtained by separating, purifying and drying. The modified heterocyclic aramid fiber prepared above and the epoxy resin bisphenol A type epoxy resin E-44 were dissolved in propylene glycol methyl ether, added to the reaction kettle and reacted with the surfactant at 70 ° C for 3.5 hours, and then polyethylene was added. Add polyamine to carry out addition reaction, add butyl glycidyl ether to cap the adduct, after the reaction, cool down to 50 ℃ and add glacial acetic acid to adjust the hydrophilic-lipophilic balance, and distill out the solvent under reduced pressure to obtain overrun Polyurethane modified heterocyclic aramid fiber epoxy resin curing agent.
步骤三，制备层间粘结材料。向环氧树脂中添加上述超支化聚氨酯改性杂环芳纶纤维环氧树脂固化剂制备环氧树脂复合粘结材料，高速搅拌混合均匀，即得到可常温固化的耐高温高粘高强高韧环氧树脂复合层间粘结材料。Step 3, prepare the interlayer bonding material. Add the above hyperbranched polyurethane modified heterocyclic aramid fiber epoxy resin curing agent to epoxy resin to prepare epoxy resin composite bonding material, stir and mix at high speed, and obtain a high temperature resistant, high viscosity, high strength and high toughness ring that can be cured at room temperature Oxygen resin composite interlayer bonding material.
为验证层间粘结材料的拉伸强度、断裂伸长率、低温柔性以及层间抗剪切和抗拉拔强度，依据《建筑防水涂料试验方法》(GB/T 16777-2008)和《树脂浇注体性能试验方法》(GB/T 2567-2008)等的相关规定对本发明实施例及对比例中所制得层间粘结材料进行基本性能试验和室内模拟试验，结果如表1所示。In order to verify the tensile strength, elongation at break, low temperature flexibility and interlaminar shear and pull-out strength of the interlayer bonding material, according to "Test Methods for Building Waterproof Coatings" (GB/T 16777-2008) and "Resin The basic performance test and indoor simulation test of the interlayer bonding materials prepared in the examples and comparative examples of the present invention are carried out in accordance with relevant regulations such as "Test Method for Casting Body Performance" (GB/T 2567-2008), and the results are shown in Table 1.
表1各实施例和对比例的性能试验结果Table 1 Performance test results of each embodiment and comparative example
根据表1：(A)分析对比例1～7可知，与未经改性处理的环氧树脂相比，超支聚氨酯和杂环芳纶纤维分别能改善环氧树脂的韧性和强度；但是随着超支聚氨酯数量的增加，复合材料拉伸强度明显减小，其量达到一定值后断裂伸长率增长减缓；随着杂环芳纶纤维数量的增加，复合材料断裂伸长率明显减小，其量达到一定值后拉伸强度增长减缓。According to Table 1: (A) Analysis of Comparative Examples 1 to 7, compared with unmodified epoxy resin, hyperbranched polyurethane and heterocyclic aramid fiber can improve the toughness and strength of epoxy resin respectively; With the increase of the amount of hyperbranched polyurethane, the tensile strength of the composite material decreases significantly, and the elongation at break growth slows down when the amount reaches a certain value; When the amount reaches a certain value, the increase of tensile strength slows down.
(B)分析对比例4和对比例5可知，与直接采用超支聚氨酯和杂环芳纶纤维改性的环氧树脂相比，将超支聚氨酯接枝到杂环芳纶纤维表面后用于改性环氧树脂所得层间粘结材料具有更加优异的强度和韧性；因为接枝超支化聚氨酯能明显改性杂环芳纶纤维表面活性，超支化聚氨酯表面具有大量活性基团，能有效提高其与环氧树脂间的粘接效果；且超支化聚氨酯具有优越的柔韧性和耐低温性能，改善了纤维的柔韧性。(B) Analysis of Comparative Example 4 and Comparative Example 5 shows that compared with the epoxy resin modified directly with hyperbranched polyurethane and heterocyclic aramid fiber, the hyperbranched polyurethane is grafted to the surface of the heterocyclic aramid fiber for modification. The interlayer bonding material obtained from epoxy resin has more excellent strength and toughness; because the grafted hyperbranched polyurethane can significantly modify the surface activity of the heterocyclic aramid fiber, and the surface of the hyperbranched polyurethane has a large number of active groups, which can effectively improve its interaction with the heterocyclic aramid fiber. The bonding effect between epoxy resins; and hyperbranched polyurethane has superior flexibility and low temperature resistance, which improves the flexibility of fibers.
(C)分析对比例5和实施例2可知，与仅将接枝超支聚氨酯的杂环芳纶纤维和三乙烯四胺直接添加到环氧树脂中制备的层间粘结材料相比，耐高温高粘高强高韧层间粘结材料粘结性能、强度和韧性得到进一步提升；因为将多乙烯多胺接枝到改性杂环芳纶纤维上，使其在与环氧树脂进行物理交联的同时与环氧树脂产生化学键的结合环氧树脂固化，纤维与树脂黏结更加紧密和稳定，使得超支聚氨酯和杂环芳纶纤维的各项优异性能的到充分的发挥。(C) Analysis of Comparative Example 5 and Example 2 shows that compared with the interlayer bonding material prepared by directly adding the heterocyclic aramid fiber and triethylenetetramine to the epoxy resin grafted hyperbranched polyurethane, the high temperature resistance The bonding performance, strength and toughness of high-viscosity, high-strength and high-toughness interlayer bonding materials are further improved; because polyethylene polyamines are grafted onto modified heterocyclic aramid fibers, they are physically cross-linked with epoxy resins. At the same time, the epoxy resin is cured with the combination of chemical bonds with the epoxy resin, and the bonding between the fiber and the resin is more tight and stable, so that the excellent properties of the hyperbranched polyurethane and the heterocyclic aramid fiber can be fully exerted.
(D)分析实施例1～9和对比例1可知，与未经改性处理的环氧树脂相比，本发明制备的耐高温高粘高强高韧层间粘结材料，拉伸强度和断裂伸长率均明显提高，说明材料黏结性能、强度和韧性提高；-20℃，90°条件下弯曲不开裂，说明材料的低温抗裂能力韧性增强；高温(60℃)条件下复合件拉拔强度与复合件剪切强度与常温(25℃)条件相比下降并不明显，说明材料耐高温性能增强。(D) Analysis of Examples 1 to 9 and Comparative Example 1 shows that, compared with the unmodified epoxy resin, the high-temperature, high-viscosity, high-strength and high-toughness interlaminar bonding materials prepared by the present invention have higher tensile strength and fracture The elongation was significantly improved, indicating that the bonding performance, strength and toughness of the material were improved; under the conditions of -20°C and 90°, the bending did not crack, indicating that the low-temperature crack resistance and toughness of the material were enhanced; the composite part was drawn under the condition of high temperature (60°C). Compared with the normal temperature (25°C), the strength and shear strength of the composite parts did not decrease significantly, indicating that the high temperature resistance of the material was enhanced.
(E)分析实施例2和对比例8可知，采用超声波处理得到的复合材料拉伸强度、断裂伸长率以及层间剪切拉拔强度与未使用超声波处理制备的复合材料相比得到明显提升，采用超声波处理纳米级杂环芳纶纤维使其具有在机械搅拌下无法达到的均匀分散和接触反应效果，使得超支聚氨酯和杂环芳纶纤维各项优异性能得到充分发挥的同时起到协同增强作用，制得性能优异的层间粘结材料。(E) Analysis of Example 2 and Comparative Example 8 shows that the tensile strength, elongation at break and interlaminar shear pull-out strength of the composites obtained by ultrasonic treatment are significantly improved compared with those prepared without ultrasonic treatment. , Ultrasonic treatment of nano-heterocyclic aramid fibers makes it have uniform dispersion and contact reaction effects that cannot be achieved under mechanical stirring, so that the excellent properties of hyperbranched polyurethane and heterocyclic aramid fibers can be fully exerted and synergistically enhanced. function to obtain an interlayer adhesive material with excellent performance.
(F)对比实施例1～9和对比例6～7的各项指标，可以发现综合各项性能指标实施例2性能最佳优异，最佳原材料组成为：聚四氢呋喃醚二醇(PTMG，Mn＝1000)18份、异佛尔酮二异氰酸酯(IP-DI)7份、丁二酸酐7份、二乙醇胺8份、三羟甲基丙烷5份、杂环芳纶纤维35份、环氧树脂100份、三乙烯四胺12份。(F) comparing the indexes of Examples 1 to 9 and Comparative Examples 6 to 7, it can be found that the performance of the embodiment 2 is the best and the best, and the best raw material is composed of: polytetrahydrofuran ether glycol (PTMG, Mn =1000) 18 parts, isophorone diisocyanate (IP-DI) 7 parts, succinic anhydride 7 parts, diethanolamine 8 parts, trimethylolpropane 5 parts, heterocyclic aramid fiber 35 parts, epoxy resin 100 parts and 12 parts of triethylenetetramine.
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