CN1348971A - Reversible epoxy resin gel and its curing agent - Google Patents
Reversible epoxy resin gel and its curing agent Download PDFInfo
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- CN1348971A CN1348971A CN 00129791 CN00129791A CN1348971A CN 1348971 A CN1348971 A CN 1348971A CN 00129791 CN00129791 CN 00129791 CN 00129791 A CN00129791 A CN 00129791A CN 1348971 A CN1348971 A CN 1348971A
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- reversible gel
- epoxy
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- 230000002441 reversible effect Effects 0.000 title claims abstract description 42
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 title claims description 27
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 57
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920006389 polyphenyl polymer Polymers 0.000 claims abstract description 17
- -1 glycidyl ester Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000012745 toughening agent Substances 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- 239000004952 Polyamide Substances 0.000 claims 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 2
- 239000003085 diluting agent Substances 0.000 claims 2
- 229920002647 polyamide Polymers 0.000 claims 2
- 239000012744 reinforcing agent Substances 0.000 claims 2
- 239000002879 Lewis base Substances 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 125000005234 alkyl aluminium group Chemical group 0.000 claims 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 claims 1
- 150000007527 lewis bases Chemical class 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000002685 polymerization catalyst Substances 0.000 claims 1
- 150000007519 polyprotic acids Polymers 0.000 claims 1
- 229920006295 polythiol Polymers 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000000518 rheometry Methods 0.000 abstract description 3
- 239000003566 sealing material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000007650 screen-printing Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000004382 potting Methods 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 description 56
- 239000000499 gel Substances 0.000 description 45
- 238000010008 shearing Methods 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008431 aliphatic amides Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000012721 stereospecific polymerization Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001442 methylidyne group Chemical group [H]C#[*] 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
一种环氧树脂可逆凝胶及其固化物,其中所说环氧树脂可逆凝胶含有100份重量的环氧树脂和1－10份重量的高全同立构聚苯基缩水甘油醚。本发明的环氧树脂可逆凝胶可用于控制树脂体系的流变性,其固化物可以应用于复合材料基体树脂、涂料、胶粘剂、筛网印刷油墨、密封材料、灌封材料等领域中,具有抗流淌,韧性高,储存稳定性好等优点。An epoxy resin reversible gel and its cured product, wherein the epoxy resin reversible gel contains 100 parts by weight of epoxy resin and 1-10 parts by weight of high isotactic polyphenyl glycidyl ether. The epoxy resin reversible gel of the present invention can be used to control the rheology of the resin system, and its cured product can be applied to the fields of composite material matrix resin, coating, adhesive, screen printing ink, sealing material, potting material, etc. Flow, high toughness, good storage stability and so on.
Description
The present invention relates to a kind of Resins, epoxy reversible gel and cured article thereof.
Many polymers can form reversible gel in appropriate solvent.Known reversible gel system has gelatin/water, polyvinyl chloride/dibutyl phthalate, polystyrene/dithiocarbonic anhydride, complete same polymethylmethacrylate/toluene etc.
When Resins, epoxy was applied to composite matrix resin, coating, tackiness agent, sealing material, rheological characteristics was crucial.For example the tackiness agent that uses on the auto production line requires to flow easily in the pipeline of sizing applicator, and does not trickle when solidifying.The tackiness agent loss can cause starved and pollution in solidification process.For tackiness agent can be dropped down in anti-current, need it to have certain yielding stress, method commonly used is to introduce suitable mineral filler in tackiness agent, as white carbon black, drops down additive as anti-current.There is the unsettled shortcoming of rheological characteristics in such system, often sag resistance variation gradually after storing for some time.
Propose among the CN1156166A to drop down properties-correcting agent as the anti-current of epoxyn with polybutyl terapthalate or its segmented copolymer; The shortcoming of this technology is, heating at high temperature is dissolved in the process of Resins, epoxy polybutyl terapthalate or its segmented copolymer, easy and the Resins, epoxy generation transesterification reaction of polybutyl terapthalate or its segmented copolymer, so rheological property is difficult for repeating.
The purpose of this invention is to provide a kind of Resins, epoxy reversible gel and cured article thereof, the repetition performance of this reversible gel is good, and is difficult for trickling when solidifying.
The inventor finds that under study for action high isotaxy polyphenyl glycidyl ether/epoxy-resin systems can form reversible gel.This novel reversible gel has the rheological properties of reversible gel, can be cured with various epoxy curing agents, and be difficult for trickling when solidifying, and the toughness of cured product increases, and therefore many important purposes are arranged.
Resins, epoxy reversible gel provided by the present invention contains the Resins, epoxy of 100 parts of weight and the high isotaxy polyphenyl glycidyl ether of 1-10 part weight.
Employed Resins, epoxy is the resin that contains two above epoxy group(ing) in the molecule in the Resins, epoxy reversible gel provided by the present invention, comprises bisphenol A type epoxy resin, novolac epoxy, polyprotonic acid glycidyl ester, amino polyfunctional epoxy resin and cycloaliphatic epoxy resin.They can use separately, also can several mixed with resin use.Also can adopt modified epoxy.
Employed high isotaxy polyphenyl glycidyl ether can be obtained by phenyl glycidyl ether polymerization under the effect of catalyst for stereospecific polymerization in the Resins, epoxy reversible gel provided by the present invention.Catalyst for stereospecific polymerization can be bimetal oxygen connection alkoxide, organotin-alkylphosphonic acid carboxylic acid ester condensates, aluminum alkyls or zinc alkyl(s).Said high isotaxy polyphenyl glycidyl ether according to its fusing point of difference of the kind of catalyzer and reaction conditions between 170-220 ℃; Its warp
13The isotaxy degree that C-NMR measures is (measuring method with reference to J.C.Roda et al, Polymer, 36 (3): 471-478,1995) more than 50%; It is solvent with the sym.-tetrachloroethane, and 30 ℃ of intrinsic viscosities of measuring down are 0.1-2.0dL/g (intrinsic viscosity testing method reference: polymer experimental technique, P22-34, press of Fudan University 1996).
According to the requirement to rheological characteristics, the amount of the high isotaxy polyphenyl glycidyl ether that adds in per 100 parts of (weight) Resins, epoxy of Resins, epoxy reversible gel of the present invention changes in 1-10 part (weight) scope.High isotaxy polyphenyl glycidyl ether content can not form gel when being lower than 1 part of weight; Formed gel was too hard when high isotaxy polyphenyl glycidyl ether content was higher than 10 parts of weight, was not easy to use.
Resins, epoxy reversible gel provided by the present invention can further contain additives such as toughener, filler, toughner, thinner as required, and these additives determine that according to prior art the present invention has no particular limits it.
The preparation method of Resins, epoxy reversible gel provided by the present invention be mixture with high isotaxy polyphenyl glycidyl ether and Resins, epoxy 170 ℃ of-250 ℃ of following heating for dissolving, directly be cooled to room temperature then or lower temperature makes it to form gel.
Resins, epoxy reversible gel of the present invention can be cured with various epoxy curing agents, obtains Resins, epoxy reversible gel cured article of the present invention, and this cured article contains the said Resins, epoxy reversible gel of 100 parts of weight and the solidifying agent of 1-100 part weight.Wherein said solidifying agent can be employed various epoxy curing agents in the prior art, comprise aliphatic amide (as the reaction product of quadrol, hexanediamine, Diethylenetriaminee (DETA), triethylenetetramine, polyethylene polyamine, Meng alkane diamines, m-xylene diamine etc. and aliphatic amide), aromatic amine is (as mphenylenediamine, 4,4 '-two amido ditanes, 4,4 '-two amido sulfobenzides etc. and composition thereof), Dyhard RU 100, Versamid is (as 200
#, 300
#, 650
#Deng trade mark Versamid), acid anhydrides is (as br dilute anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl-3,6 bridge inner methylidyne tetrahydric phthalic anhydrides etc.), Lewis acid (as boron trifluoride-ethamine complex compound etc.), Lewis alkali is (as dimethyl benzyl amine or 2,4, tertiary amine compounds such as 6-three dimethyl amine methylphenols etc.), multi-thioalcohol compound etc.Also can add toughener, filler, toughner, thinner etc. in actual applications according to service requirements.
Resins, epoxy reversible gel of the present invention and cured article thereof can be applied to especially have the occasion of strict demand to adopt Resins, epoxy reversible gel of the present invention very favourable to rheological characteristics in the fields such as composite matrix resin, coating, tackiness agent, screen printing printing ink, sealing material.
The present invention adopts high isotaxy polyphenyl glycidyl ether and Resins, epoxy to form reversible gel.Since polyethers not can with Resins, epoxy generation transesterify, therefore the performance repeatability of the reversible gel that forms is fine.In addition, the advantage of Resins, epoxy reversible gel of the present invention also has, and only needs a spot of high isotaxy polyphenyl glycidyl ether just can make Resins, epoxy have enough yielding stresses, to prevent resin trickling when solidifying.And high isotaxy polyphenyl glycidyl ether has good toughening effect to Resins, epoxy.
Resins, epoxy reversible gel of the present invention is a reversible for heating, and high isotaxy polyphenyl glycidyl ether is dissolved in the Resins, epoxy when also promptly heating, and cooling back system becomes gel, and reheat dissolves again.
Resins, epoxy reversible gel of the present invention has the rheological properties of gel.They have significant yielding stress; System shows very high viscosity under low shear rate, along with the increased viscosity of shearing rate reduces rapidly.
Resins, epoxy reversible gel cured article of the present invention is because the existence of high isotaxy polyphenyl glycidyl ether has than pure epoxy resin better toughness.Application in structure unit has important meaning for Resins, epoxy in the raising of fracture toughness property.
Below will the present invention is described further by embodiment.Except as otherwise noted, used chemical reagent is the commercial goods in each embodiment and the Comparative Examples.
Embodiment 1
100 gram phenyl glycidyl ethers are joined alkoxide (molecular formula: ((i-C at 3.5 gram aluminium-zinc bimetal oxygen
3H
7O)
2AlO)
2Zn) polymerization 2 hours under 100 ℃, anhydrous and oxygen-free condition in 150 milliliters of toluene under the katalysis, with the insoluble product that obtains behind the acetone extract is high isotaxy polyphenyl glycidyl ether (being designated as i-PPGE-1), its diad degree of isotacticity is 82%, fusing point is 180-190 ℃, and 30 ℃ of following intrinsic viscosities are 0.6dL/g in tetrachloroethane.100 gram Resins, epoxy E-51 and 5 are restrained above-mentioned i-PPGE-1 mix, stir down at 200 ℃ and obtain clear solution.Above-mentioned solution directly is cooled to room temperature promptly obtains translucent gel.Bright this gelling system of static rheology meter presents tangible shear shinning phenomenon, is 10 in shearing rate
-2s
-1The time viscosity be 5 * 10
5Pa.s is 10 in shearing rate
2s
-1The time viscosity be 5 * 10
3Pa.s.The yielding stress of this gel under 25 ℃ is 320Pa (rheological property and yielding stress test reference literature: Xia Wang et al, Journal of Materials Science 32111-114 (1997)).The dynamic rheological property measurement shows that system has the feature of gel.
Comparative Examples 1
5.0 gram polybutylene terephthalates (PBT101, Research Inst. of Chemical Industry, Beijing) are stirred down at 220 ℃, make it to be dissolved in the 100 gram Resins, epoxy.Solution after 4 hours, is cooled to room temperature 180 ℃ of maintenances.Static rheology meter is bright: the shear shinning phenomenon of system is not obvious, and the dynamic rheological property measurement shows: the Resins, epoxy of this moment does not have the feature of gel.
When adding the polybutylene terephthalate of 7.5 weight % in Resins, epoxy, system presents tangible shear shinning phenomenon.The dynamic rheological property measurement shows: the Resins, epoxy of this moment has the feature of gel.
This Comparative Examples explanation when dropping down properties-correcting agent and prepare epoxy resin gel as anti-current with polybutylene terephthalate, the polybutylene terephthalate that needs are relatively large.
Embodiment 2
5 gram i-PPGE-1 of preparation among E51 Resins, epoxy 100 grams and the embodiment 1 are stirred to dissolving fully under 200 ℃, be cooled to 130 ℃ then, add solidifying agent 4 again, 4 '-diaminodiphenylsulfone(DDS) (DDS) 32 grams, heating is stirred down to make after the DDS dissolving resin compound poured into and is solidified in the mould, condition of cure is 125 ℃/2 hours, 200 ℃/2 hours.
After the sample solidifies, the energy-to-break that adopts three-point bending method to record cured article is 350J/m
2(fracture toughness property is measured with reference to ASTM E399-90), the second-order transition temperature that records cured article by dsc is 193 ℃ (second-order transition temperature testing method references: polymer experimental technique, P125-134, press of Fudan University 1996).
Comparative Examples 2
E51 Resins, epoxy 100 gram is heated to 130 ℃, adds solidifying agent 4,4 32 grams, heating is stirred down to make after the DDS dissolving resin compound poured into and is solidified in the preheated mold, and condition of cure is 125 ℃/2 hours, 200 ℃/2 hours.
After the sample solidifies, adopting the energy-to-break of three-point bending method test cured article is 146J/m
2, be 199 ℃ by the second-order transition temperature of dsc test cured article.
Embodiment 3
E51 Resins, epoxy 100 grams are stirred to dissolving fully with 3 gram i-PPGE-1 under 200 ℃.Obtain translucent gel after being cooled to room temperature.In above-mentioned gel, add solidifying agent diethylenetriamine 12 grams.Mix the back and on steel plate, make 100mm * 10mm * 1mm adhesive tape.Trickling distance＜0.1cm after vertically placing 2 days under 30 ℃.Bonding 45# steel disc, 30 ℃ solidify down that shearing resistance is 13.5MPa (shearing resistance is measured with reference to GB7124-86) after 2 days.
Comparative Examples 3
E51 Resins, epoxy 100 grams are mixed the back with solidifying agent diethylenetriamine 12 grams on steel plate, make 100mm * 10mm * 1mm adhesive tape.Trickling distance＞15cm after vertically placing 2 days under 30 ℃.Bonding 45# steel disc, 30 ℃ solidify down that shearing resistance is 7.7MPa after 2 days.
Embodiment 4
E51 Resins, epoxy 100 grams are stirred to dissolving fully with 3 gram i-PPGE-1 under 200 ℃.Obtain translucent gel after being cooled to room temperature.Adding solidifying agent 4,4 in above-mentioned gel '-diaminodiphenylmethane 25 grams.Mix the back and on steel plate, make 100mm * 10mm * 1mm adhesive tape.Vertically be placed in 100 ℃ of baking ovens, the trickling distance is 0.8cm behind the resin solidification.Bonding 45# steel disc, at room temperature testing shearing resistance after the curing in 120 ℃/2 hours is 19.6MPa.
Comparative Examples 4
With E51 Resins, epoxy 100 gram and solidifying agent 4,4 '-diaminodiphenylmethane 25 grams mix the back and make 100mm * 10mm * 1mm adhesive tape on steel plates.Vertically be placed on the distance＞15cm that trickles behind the resin solidification in 100 ℃ of baking ovens.Bonding 45# steel disc is at room temperature tested shearing resistance 10.6MPa after the curing in 120 ℃/2 hours.
Embodiment 5
With phenyl glycidyl ether 100 grams, Bu
2SnO-Bu
3PO
4Condenses catalyzer 0.1 gram and benzene 40ml mix back flow reaction 1 hour.With the insoluble product that acetone extract obtains, after 140 ℃ of vacuum-drying, obtain high complete same polyphenyl glycidyl ether, be designated as i-PPGE-2.Productive rate is 96%, and its diad degree of isotacticity is 86%, and fusing point is 199-204 ℃.
100 gram Resins, epoxy E-51 and 5 are restrained above-mentioned i-PPGE-2 mix, stir down at 200 ℃ and obtain clear solution.Above-mentioned solution directly is cooled to room temperature promptly obtains translucent gel.This gel is made 100mm * 10mm * 1mm adhesive tape on steel plate, vertically be placed on do not occur after 3 days in 60 ℃ of baking ovens the trickling.
Embodiment 6
With E51 Resins, epoxy 100 gram and molecular weight is that 1000 hydroxy-terminated polytetrahydrofuran 30 grams are at Bu
2SnO-Bu
3PO
4Modified epoxy (oxirane value is 0.288) is made in the effect of condenses catalyzer reaction down.Above-mentioned modified epoxy is mixed with 3 gram i-PPGE-2.Being heated to i-PPGE-2 at 200 ℃ dissolves fully.Be cooled to room temperature and promptly obtain the modified epoxy gel.Prepare tackiness agent by the proportioning in the table 1.Bonding 45# steel disc solidifies the back and measures shearing resistance.Performance data sees Table 1.Table 1
| Modified epoxy gel (parts by weight) | Solidifying agent (parts by weight) | Condition of cure | Shearing resistance (MPa) |
| ????133 ????133 ????133 | Triethylene tetramine (6.1) dicyanamide (9.0) 4,4 '-diaminodiphenylmethane (18.5) | ?60℃/3h ?160℃/3h ?100℃/2h | ????30.4 ????37.1 ????30.5 |
Comparative Examples 5
With E51 Resins, epoxy 100 gram and molecular weight is that 1000 hydroxy-terminated polytetrahydrofuran 30 grams are at Bu
2SnO-Bu
3PO
4Modified epoxy (oxirane value is 0.288) is made in the effect of condenses catalyzer reaction down.
Prepare tackiness agent by the proportioning in the table 2.Bonding 45# steel disc solidifies the back and measures shearing resistance.Performance data sees Table 2.Table 2
| Modified epoxy (parts by weight) | Solidifying agent (parts by weight) | Condition of cure | Shearing resistance (MPa) |
| ????130 ????130 ????130 | Triethylene tetramine (6.1) dicyanamide (9.0) 4,4 '-diaminodiphenylmethane (18.5) | ?60℃/3h ?160℃/3h ?100℃/2h | ????24.5 ????31.1 ????23.8 |
Claims (10)
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|---|---|---|---|
| CNB001297910A CN1184261C (en) | 2000-10-13 | 2000-10-13 | Reversible epoxy resin gel and its curing agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001297910A CN1184261C (en) | 2000-10-13 | 2000-10-13 | Reversible epoxy resin gel and its curing agent |
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| Publication Number | Publication Date |
|---|---|
| CN1348971A true CN1348971A (en) | 2002-05-15 |
| CN1184261C CN1184261C (en) | 2005-01-12 |
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| CN (1) | CN1184261C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104869954A (en) * | 2012-12-14 | 2015-08-26 | 南加利福尼亚大学阿尔弗雷德·E·曼恩生物医学工程研究所 | Adhesive articles |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104869954A (en) * | 2012-12-14 | 2015-08-26 | 南加利福尼亚大学阿尔弗雷德·E·曼恩生物医学工程研究所 | Adhesive articles |
| US10098790B2 (en) | 2012-12-14 | 2018-10-16 | University Of Southern California | Adhesive articles |
| CN104869954B (en) * | 2012-12-14 | 2019-03-01 | 南加利福尼亚大学阿尔弗雷德·E·曼恩生物医学工程研究所 | Adhesive article |
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