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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Abstract
An epoxy resin reversible gel and its solidified substance have the above-mentioned gel containing 100 wt. portions of epoxy resin and 1-10 wt. portions of high-full common space polyphenyl glycidic ether. This invented gel can be used for controlling the rheological property of the resin system, its solidified substance can be applied to the fields of composite material matrin resin, coating, adhesive, screen printing ink, sealing material and encapsulating material, and has the advantages of anti-flowability, high tenacity and good storing stability.
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)
1, a kind of Resins, epoxy reversible gel contains the Resins, epoxy of 100 parts of weight and the high isotaxy polyphenyl glycidyl ether of 1-10 part weight.
2, according to the Resins, epoxy reversible gel of claim 1, wherein said Resins, epoxy is the resin that contains two above epoxy group(ing) in the molecule.
3, according to the Resins, epoxy reversible gel of claim 2, wherein said Resins, epoxy is bisphenol A type epoxy resin, novolac epoxy, polyprotonic acid glycidyl ester, amino polyfunctional epoxy resin or cycloaliphatic epoxy resin, perhaps their mixture.
4, according to the Resins, epoxy reversible gel of claim 1, the isotaxy degree of wherein said high isotaxy polyphenyl glycidyl ether is more than 50%, and intrinsic viscosity is 0.1-2.0dL/g, and fusing point is 170-220 ℃.
5, according to the Resins, epoxy reversible gel of claim 1, wherein said high isotaxy polyphenyl glycidyl ether is obtained by phenyl glycidyl ether polymerization under the effect of the catalyst for stereospecific polymerization that comprises bimetal oxygen connection alkoxide, organotin-alkylphosphonic acid carboxylic acid ester condensates, aluminum alkyls or zinc alkyl(s).
6, according to the Resins, epoxy reversible gel of claim 1, this reversible gel further contains toughener, filler, toughner or thinner.
7, a kind of Resins, epoxy reversible gel cured article, this cured article contain 1 the Resins, epoxy reversible gel of 100 parts of weight and the solidifying agent of 1-100 part weight.
8, according to the Resins, epoxy reversible gel cured article of claim 7, wherein said solidifying agent is aliphatic amide, aromatic amine, Dyhard RU 100, Versamid, acid anhydrides, Lewis acid, Lewis alkali or multi-thioalcohol compound.
9, according to the Resins, epoxy reversible gel cured article of claim 8, wherein said solidifying agent is aliphatic amide, aromatic amine, Dyhard RU 100 or Versamid.
10, according to the Resins, epoxy reversible gel cured article of claim 7, this cured article further contains toughener, filler, toughner or thinner.
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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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| 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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|---|---|---|---|
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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 |
-
2000
- 2000-10-13 CN CNB001297910A patent/CN1184261C/en not_active Expired - Lifetime
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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| CN1184261C (en) | 2005-01-12 |
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