CN1197098A - Low temp. adhesive and firming agent used for low temp. adhesive - Google Patents
Low temp. adhesive and firming agent used for low temp. adhesive Download PDFInfo
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Abstract
A low-temp adhesive is disclosed, which has very good shear strength and stable performance at low temp, ultralow temp., middle-temp and even high temp. A solidifying agent for the low-temp adhesive can form a dual-phase structure with epoxy resin and toughening agent, and features higher vibrification temp and temp impact resistance, stable properties and long storage period (more than 3 years).
Description
A kind of solidifying agent that the present invention relates to a kind of low temperature adhesive and be used for low temperature adhesive.
The research and development of low temperature adhesive and space technology and low-temperature superconducting technology are closely related, and as far back as the fifties, various research reports are arranged, patent and commerical prod.
In low temperature adhesive research, the general Resins, epoxy that uses is as structure host, yet behind the epoxy resin cure, has three-dimensional crosslinking structure, molecular structure is tight, unit elongation is lower, adhesive structure because stress distribution is inhomogeneous in the glue-line, is easy to destroy under the effect of mechanical stress and thermal stress, therefore in the adhesive system pore and fine fisssure defective can appear, under low temperature environment, the effects such as difference of the cold string stress of tackiness agent itself and the linear expansivity of tackiness agent and bonded material make these defectives even more serious, so as the low temperature structure tackiness agent, overcome the fragility of resin, most important in Study on Adhesive and application.
The epoxyn system generally all is by epoxy-resin systems, curative systems, and coupling agent system and packing material are formed, and toughness reinforcing approach also is many-sided.In different research approaches, different selections is arranged, can improve by performance said components, reach the purpose of lower temperature application.General adhesive system can not be applicable to liquid nitrogen temperature (77K) and liquid helium temperature low temperature range such as (4.2K), because under this envrionment temperature, general increasing is gentle, toughening modifying can not satisfy service requirements, in ultra-low temperature surroundings, some molecule segment freezes, and loses snappiness; Some properties-correcting agent can make its low-temperature performance improve as urethane, polymeric amide and nylon etc., but the thermotolerance of system significantly reduces, and general second-order transition temperature is below 100 ℃.
In the Resins, epoxy, comprise bisphenol A epoxide resin, ethylene oxidic ester epoxy resin and aliphatic epoxy resin, in to epoxy resin modification research, existing report all is that bisphenol A epoxide resin is carried out modification, the approach of modification mainly contains the following aspects:
1, add and dose thing: be intended to improve the thermal stress state, reach the purpose of lower temperature application, as (R.M.Mclintock et al. such as Mcclintocks, Proc.of CEC ' 57.1957) adopt aluminium powder as weighting agent, the shearing resistance of its tackiness agent is 7 MPas (MPa) under 20K.
2, polyurethane modified epoxy resin: with end is that the polyethers of isocyanic ester gives aggressiveness and bisphenol A epoxide resin mixes, be cured with amine curing agent, this tackiness agent low-temperature performance good (H.Leeand K.Neville, ＂ Handbook of Epoxy Resin ＂, McGraw-Hill, New Youk, 15,11,1967).But this end contains the compound of isocyanate group, to damp and hot all very responsive, uses to be subjected to certain limitation.Kroes Nai Er (Rex.B.Crosnel et al., Macromol.Sci.Chem., A3 (7), 1381-1393,1969) once to analyzing with the cryogenic mechanics performance of polyether-modified urethane, point out:, thereby improved low temperature flexibility under liquid nitrogen temperature because the polyethers repeating unit can make molecule rotate freely at low temperatures, even does not freeze.
3, modified nylon Resins, epoxy: the epoxyn of modified nylon is to contain the compound of a large amount of amide group and the product of Resins, epoxy generation chemical reaction in the molecule.Have good toughness at low temperatures, shearing resistance reaches 10～40 MPas during 20K, and the reaction needed of nylon and Resins, epoxy just can be finished about 170 ℃,, have significant limitation (M.B.Smith and S.E.Susman, Proc.of CEC ' 62 in the use, 300-305,1962.).
4, soft agent (also claiming flexible dose) modified epoxy: it is that aliphatic tricarboxylic acids increases gentle bisphenol A epoxide resin that the seventies U.S. makes one of low-temperature composite material adhesive system with the most use NASA2, with the succinyl oxide is solidifying agent, benzyldimethylamine is a promotor, its low-temperature performance is good, poor (the L.M.Soffer and R.Molho of room-temperature property, NASA CR-72114,1967) the tetrahydrofuran (THF) polyethers also can be used as flexibilizing agent, the low temperature glue product that DW-3 glue is fastened extra large synthetic resins Research Institute and sold, by tetrahydrofuran (THF) modified bisphenol A epoxy resin, modified amine 590 solidifying agent, KH550 (end amido siloxanes compound) is a coupling agent; 590 solidifying agent are to be made by mphenylenediamine and phenyl glycidyl ether.When solidifying for 60 ℃, the shearing resistance of 77K is greater than 19.6 MPas, and the subject matter of this glue is that shearing resistance descends rapidly after being higher than room temperature, is 7.6 MPas in the time of 60 ℃; The zero pour of solidifying agent is 293K (20 ℃), is easy to moisture absorption whiting, brings inconvenience to use.
6, inflexible bisphenol A epoxide resin-curative systems, E-787 (Polaris) and the used tackiness agent of G-11 glass filament reinforced plastics as the U.S. all are to belong to this class system, low temperature down cut intensity is lower with respect to room temperature, be not have the flexible resin system (Vol 24 for M.B.Kasen, Advan.Cryo.Eng., 63-73,1977).
Above content is the modification by Resins, epoxy, it is gentle that it is increased, or the rigidity system of directly using price height, complex process reaches the purpose that low temperature uses, and also is to improve one of Resins, epoxy low-temperature performance approach by adopting the snappiness solidifying agent to come modified epoxy.Increase the gentle following several respects that have with solidifying agent in the prior art:
1, Versamid is as solidifying agent, this type of Versamid is a kind of thick liquid that linoleic acid dimer and aliphatic polyamine reaction generate, it can generate with the Resins, epoxy effect has certain flexible adhesive system, this is because long fatty carbon chain is arranged in the polymeric amide molecule, plays inner toughening effect.Under low temperature environment, bisphenol A epoxide resin polymeric amide tackiness agent mechanical property is relatively disperseed, and has medium tenacity, should not use (Vol 24 for M.B.Kasen, Advan.Cryo.Eng., 63-73,1977) as the structure jelly.
2, flexible solidifying agent: Ai Wensi proposes with ending amino polyether as curing agent for epoxy resin, the adhesive system that bisphenol a resin and polyoxytrimethylene ether diamine (molecular weight 230-2000) have obtained to have certain flexibility, and point out: common at low temperatures toughner is to improving inoperative (the D.Evans and J.T.Morgan of fragility, Nonmetallic Materials and Composites at Lowtempertatures, vol 2,73-87,1980.).
Except bisphenol A epoxide resin from various approach modifications, amine hardener is toughness reinforcing, increase outside the mode such as gentle, select ethylene oxidic ester epoxy resin with 4,4 '-diaminodiphenyl-methane solidifies, acquisition has the adhesive system of good low temperature properties, this Resins, epoxy comprises the trimesic acid three-glycidyl ester, terephthalic acid diglycidyl ester etc., both are respectively 20.5 at shearing resistance when 4.2K, 15.9 MPa, shearing resistance is respectively 19.0 during 77K, 23.6 MPa, be respectively 19.0 during 300K, 19.5 MPa, be the adhesive system that in wide warm area, to use (Yang Yukun etc., " synthetic adhesive ", 295 pages, Science Press, 1980; M.W.Ranney, ＂ Epoxy and UrethaneAdhesives ＂, Noyes Data, U.S.A., 4,1971; S.R.Sandler, J.Appl.Polym.Sci.11, (3), 465,1967), but used Resins, epoxy and the solidifying agent of this tackiness agent is solid, and preparation technology is very complicated, cold-resistant thermal shocking is indifferent, and problem such as the obstacle that has living space, unless just have special requirement to use.
Increase in the soft toughness reinforcing approach above-mentioned, each component is mixed can be cured reaction, formed cured article is a uniform system, because the influence of subsurface defect or thermal stress, above-mentioned adhesive system intensity when room temperature and the above temperature of room temperature reduce or low temperature under still show fragility, this for a long time always the modification approach of research be dissatisfactory.The load of the large-scale superconduction of picture supports, they all will stand low temperature simultaneously still to middle temperature even pyritous influence at the spacecraft of upper space operation, picture load bracing member, not only bear weight at low temperatures, under other temperature condition, bear weight equally, and standing the variation of repetitiousness hot-cool environment, all there are distinct disadvantage in many flexible systems and rigidity system.
Since sixties Mo, the liquid acrylonitrile butadiene rubber with active group (end group) is epoxy resin toughened, and the rubber toughened epoxy-resin systems that is generated is a two phase structure, and having with Resins, epoxy is external phase, is the microtexture of disperse phase with the rubber elastomer.The generation of this system has improved toughness, but second-order transition temperature descends seldom.
Adopt the research and the existing many reports of application of elastic body toughening Resins, epoxy, people such as De Dike (H.Dodiuk, et al., Composites, Vol.22,4,319-327,1991) epoxy resin toughened with amino terminated butadiene acrylonitrile rubber (ATBN), this glue is ambient temperature curable, when 243K, shearing resistance reaches more than the 20MPa.Wa Erke (J.M.Walker et al., Modern Plastics, 62-64,1976) with nbr carboxyl terminal (CTBN) modified epoxy, as Embedding Material, measure modification front and back tension force and flexural strength, the adhesive system mechanical property through modification when 219K all has improvement.Though relevant both at home and abroad rubber toughened research and commercial tackiness agent kind are a lot, minimum temperature does not all surpass above-mentioned scope, uses with desired ultra-low temperature surroundings to differ greatly, and this is to determine because of its molecular structure.
Except paracril is epoxy resin toughened, also has use side carboxyl polyethers, comprise different types of elastomericss such as end carboxyl tetrahydrofuran (THF) epoxy propane copolymer (CTCPE), end carboxyl propylene glycol copolymers, these elastic body toughening Resins, epoxy all can generate two phase structure.Above-mentioned elastomeric common feature is to contain end active group amido or carboxyl, can reach molten altogether with Resins, epoxy.By toughening modifying layer-to-layer adhesion intensity is improved, cold-and-heat resistent impact and anti-cracking performance are improved.Heat-drawn wire and second-order transition temperature then descend seldom, and other relevant performance is except individual cases, and anti-intensity, the flexural strength of stretching has in various degree raising before more not toughness reinforcing.In toughness reinforcing research, the minimum temperature scope that relates to does not have the more research and application report of cold zone more than 213K (60 ℃).
In above-mentioned toughened system, employed solidifying agent mostly is liquid acid anhydrides, 2-ethyl-4-methylimidazole, hexahydropyridine, trolamine, and amine curing agent has only the application report of diaminodiphenylsulfone(DDS) (DDS).
In sum, the method of research epoxy resin roughening modification has two kinds: the one, adopt the method that increases Resins, epoxy molecule segment flexibility, being actually a kind of is that increasing of cost is gentle to sacrifice the system thermal characteristics, as epoxy-nylon, epoxy-polymeric amide, epoxy-polyurethane modified system heat-drawn wire at 80～100 ℃.Because middle gentle high-temperature behavior is too poor, though low-temperature performance is better, it is not satisfied in use still to seem.The 2nd, with the method that forms two phase structure, improve the toughness of system, and less to the thermal characteristics influence.But applied research still is blank under the low temperature, particularly very low temperature.
Kind surplus the modified amine curing agent of delivering both at home and abroad nearly ten, see from existing lower temperature application: 590 solidifying agent (Shanghai Resin Factory's production) are the condensess of mphenylenediamine and propylene oxide phenyl ether, Huang or brownish black thick liquid, 20 ℃ at zero pour, using has small-particle often, need firmly stir well even, easily oxidation, whiting in air, influence actual service life,, usually in some months, lost efficacy as DW-3 ultra-low temperature glue stick solidifying agent.All the other modified amine there is no the report of lower temperature application.The kind of modified amine has 593,591,120,701,702,703, Gy051,105 amine that contract, 708 etc.
What will mention in addition is several aromatic amine curing agents, they are solid mphenylenediamines (63 ℃ of fusing points), 4,4 '-diaminodiphenylmethane (fusing point is 85 ℃) and 4,4 '-diaminodiphenylsulfone(DDS) (175 ℃ of fusing points), aromatic amine curing agent is better than aliphatic amide performance as lower temperature application, but the fusing point height is solid, the solidification value height, use inconvenient, the technological operation complexity unless special low temperature and high temperature requirement are arranged, is not generally used.Adopt the tackiness agent of this class solidifying agent that H-006 is arranged, 672 low temperature glue etc., its principal feature is that heat-drawn wire exceeds tens degree (40～60 ℃) than DW-3 glue.
Because aromatic amine curing agent is necessary heat fused solid in application, operational difficulty uses inconvenience, adopts the eutectic mixture of various aromatic amines to solve problem so have.The eutectic amine curing agent of having delivered at present has following three kinds: mphenylenediamine and 4, the mixture of 4 '-diaminodiphenylmethane; Mphenylenediamine and 4,4 '-diaminodiphenylmethane and tolylene diamine mixture; Ortho-toluene diamine, toluylenediamine and 4,4 '-diaminodiphenylmethane mixture (" synthetic material industry " 1975,1).So far do not see the report of other new development.
At the deficiency of prior art, the objective of the invention is to propose a kind of low temperature adhesive, and the solidifying agent that is used for low temperature adhesive.This tackiness agent not only also has good shearing resistance at low temperature, very low temperature even at middle gentle high temperature, and stable performance, and the preparation method is simple, and raw material is easy to get.
Another object of the present invention is to propose a kind of solidifying agent, and it can use adhesive system and has higher second-order transition temperature under very low temperature, and manufacture craft is simple, stable performance, but prolonged preservation is never degenerated.
Tackiness agent provided by the invention is made up of the Resins, epoxy of (by weight) 100 parts, 14～150 parts varies solidifying agent, 0～3 part coupling agent and 5～35 parts toughner.
Said Resins, epoxy contains the bisphenol A epoxide resin of 0～100 heavy % and the ethylene oxidic ester epoxy resin of 0～100 heavy %.The oxirane value of said Resins, epoxy (equivalents of epoxy in per 100 gram Resins, epoxy) is 0.3～1.0.
Varies solidifying agent provided by the invention is by the amine condensation of 20～100 heavy %, the aromatic amine of 0～80 heavy %, the polymeric amide of 0～60 heavy % and the solidifying agent that 0～8 tertiary amine that weighs % is formed.
Said amine condensation contains primary amino and/or the secondary amino group that is connected on aromatic ring and the aliphatic chain, and wherein aromatic ring can have 0～4.Said amine condensation can be the condenses of aminated compounds; The also condenses of aminated compounds and ether compound, this ether compound can contain aromatic ring and/or aliphatic chain, as the affixture of glycidyl ether, diethylenetriamine and oxyethane butyl ether.The reactive hydrogen number of said varies is 2～6.
Said aromatic amine can contain 1～4 aromatic ring, as m-xylene diamine, and 4,4 '-diaminodiphenyl-methane, benzyldimethylamine, mphenylenediamine.The reactive hydrogen number of said aromatic amine is preferably 2～6.
The amine value of said polymeric amide is 200～400 (the amine value is that the contained unhindered amina of a gram polymeric amide is equivalent to potassium hydroxide milligram number, by Tianjin Q/HG3402-95 standard test).
Said tertiary amine nitrogen atom is connected on the aliphatic chain.
Said coupling agent is a siloxane compound, can contain the amino or end epoxy group(ing) of end.
Said toughner contains the liquid oligomer of urethane, polyester and polyether segment, can be to contain end carboxyl, end amido, terminal hydroxy group and groups such as end epoxy group(ing) and ester group.
Tackiness agent provided by the invention can be prepared by following method:
Resins, epoxy is mixed with toughner, stir and be heated to 60～120 ℃, cooling is prepared into prepolymer; Add the varies solidifying agent in proportion, after stirring, add silane coupling agent, can use after mixing, also can silane coupling agent be joined in the prepolymer of Resins, epoxy and toughner in advance, or in the varies solidifying agent.
When using tackiness agent of the present invention, gel time can be 45 minutes summer, can be 1 hour winter.The solidified temperature can be selected between 303K to 433K according to the requirement to shearing resistance, is respectively set time 72 to 2 hours.Described prepolymer stable performance, but prolonged preservation is never degenerated.
Solidifying agent provided by the invention can be prepared by following method: the amine condensation of 20～100 heavy % and the aromatic amine of 0～80 heavy % are mixed, add the tertiary amine promotor of polymeric amide and 0～8 heavy % of 0～60 heavy % again, mix.If amine condensation is or/and aromatic amine is a solid, after amine condensation and aromatic amine mix, need be heated to dissolving, as be heated to 60～150 ℃, again cooling.
Tackiness agent provided by the invention can obtain to have the two phase structure of toughness characteristics, can satisfy the application of the very low temperature scope of 4.2～77K, and higher thermal stability is arranged, can be at the wide warm area (adhesive system of using in 4.2～393K) thereby formed.Overcome prior art low temperature adhesive thermal characteristics decline problem too far, solve rubber toughened system again and be unsuitable for the problem that low temperature environment uses, shortcomings such as many rings Resins, epoxy cost high technology complexity have also been overcome, and mechanical property is good, insensitive to temperature variation, also can select suitable prescription according to different needs.
Containing urethane, polyester or polyether segment in the used toughner molecule of the present invention, is the liquid oligomer that is connected together by chemical bond-linkings such as ester bond, ammonia ester bond, ehter bonds.Hydrocarbon chain is obviously different with carbon oxygen chain with only containing in the existing toughner molecule, and it can dissolve each other with any ratio with Resins, epoxy, and is nontoxic, the non-volatility composition, and chemical property is stable, low price.Using that the used toughner of the present invention is epoxy resin toughened can be epoxy resin toughened the same with the active paracril of end, the active copolyether of end, and formation is external phase with Resins, epoxy, is the two phase structure of disperse phase with toughner, reaches the toughness reinforcing purpose of low temperature.
Solidifying agent provided by the invention can generate two phase structure with Resins, epoxy and toughner, make adhesive system have higher second-order transition temperature and cold-resistant thermal shocking ability, can use at very low temperature, be easy to preserve, be liquid, stable performance, it is rotten to be difficult for the moisture absorption, but prolonged preservation, the usage period is more than 3 years.
The characteristics of tackiness agent provided by the invention are: the raw material in the prescription is easy to get, and use technology simple, but room temperature or medium and high temperature is solidified.The characteristics of this patent resin system are the two phase structures that its formation has toughness characteristics, suitable wide temperature region (4.2 to 393K), and mechanical property is good, and is insensitive to temperature variation, cold-resistant thermal shocking, low toxicity, and can select prescription according to different needs.
To be described in further details the present invention by embodiment below.
Embodiment 1
100 gram bisphenol A epoxide resins (oxirane value 0.48-0.54) and 20 gram toughner (trade mark N, Qi Shi company produces) are mixed, stir and be heated to 80 ℃, cooling is prepared into prepolymer A.
The 50 gram Gy-051 amine (productions of Dong Zhu chemical plant) and 50 that contracts is restrained 4, and 4 '-diaminodiphenylmethane (production of Shanghai reagent three factories) mixes, and is heated to dissolving, makes solidifying agent B.
With coupling agent (KH560, chemical plant, Gai County produce) as the C component, in A: B: C=1: after 0.25: 0.015 ratio and component A and B mix.Paste sticking Ly12 aluminum metal film according to a conventional method.At 30 ℃/72 hours, 60 ℃/8 hours, under 100 ℃/4 hours the condition, aluminum metal film was heating and curing respectively.Measure different solidification value down cut intensity by national standard, it the results are shown in Table 1.
Embodiment 2
100 gram bisphenol A epoxide resins (oxirane value 0.48-0.54) and 20 gram toughner (trade mark N, Qi Shi company produces) are mixed, stir and be heated to 80 ℃, cooling is prepared into prepolymer A.
98 gram Gy-051 are contracted after amine (productions of Dong Zhu chemical plant) and 2 restrains benzyldimethylamines (production of Shanghai reagent three factories) and stir, make the B component.
With coupling agent (KH560, chemical plant, Gai County, Liaoning Province produce) as the C component, in A: B: C=1: after 0.25: 0.015 ratio and component A and B mix.Paste sticking Ly12 aluminum metal film according to a conventional method.According to the aluminum metal film that is heating and curing of the condition of cure in the example 1.Measure different solidification value down cut intensity by national standard, it the results are shown in Table 1.The tackiness agent that its performance and embodiment 1 make is close, but its casting matrix flexural strength is higher.
Embodiment 3
Method according to example 1 prepares tackiness agent, just adopts 15 gram toughner, according to same procedure it is pasted sticking Ly12 aluminum metal film, and the aluminum metal film that is heating and curing is measured different solidification value down cut intensity, and it the results are shown in Table 1.
Comparative Examples
Method according to example 1 is pasted sticking Ly12 aluminum metal film with DW-3 glue (Shanghai synthetic materials Research Institute), 303K, curing in 72 hours, and measurement 300 and 77K temperature down cut intensity, it the results are shown in Table 1.Also enumerated in the table 1 DW-1, DW-2, DW-3 and DW-4 glue (Shanghai synthetic materials Research Institute), NHJ-44 glue (7 03 developments of Ministry of Astronautics Industry), HY912 glue (Tianjin synthetic material industry Research Institute), 672 and the test piece of H-006 glue (Dalian Chemical Physics Research Institute's development) bonding aluminium after strength property (select from old seat and compile " splicing application manual ", 1994, electronic publishing society).
Table 1
| Example | Condition of cure (K/ hour) | Shearing resistance (MPa) | |||||
| Measure temperature (K) | |||||||
| ????4.2 | ????77 | ????300 | ????333 | ????373 | ????393 | ||
| ????1 | ????303/72 ????333/8 ????373/4 ????433/2 | ????13.68 ????17.35 ????19.76 ????19.34 | ????13.23 ????16.90 ????19.49 ????20.63 | ????15.48 ????19.35 ????20.45 ????21.80 | ????9.44 ????13.93 ????18.96 ????19.87 | ????3.93 ????4.24 ????10.54 ????12.72 | ?????/ ?????/ ????9.77 ????10.74 |
| ????2 | ????303/72 ????333/8 ????373/4 ????433/2 | ????/ ????/ ????/ ????/ | ????11.86 ????15.94 ????17.56 ????20.43 | ????16.73 ????17.76 ????17.84 ????20.02 | ??????/ ????15.68 ????16.45 ????22.41 | ?????/ ????9.55 ????13.45 ????17.32 | ?????/ ?????/ ????6.24 ????13.66 |
| ????3 | ????303/72 ????333/8 ????373/4 ????433/2 | ????/ ????/ ????/ ????/ | ????8.28 ????14.96 ????17.29 ????19.45 | ????14.19 ????16.83 ????17.03 ????20.29 | ????10.89 ????17.36 ????18.63 ????19.92 | ?????/ ????7.52 ????13.94 ????16.72 | ?????/ ?????/ ????12.40 ????14.34 |
| Comparative Examples | |||||||
| Comparative Examples | ????303/72 | ????/ | ????13.55 | ????13.84 | ??????/ | ?????/ | ?????/ |
| ??DW-1 | 333/2, pressurization 373/1, pressurization | ????/ ????/ | ??≥17.64 ??≥17.64 | ??≥4.90 ??≥4.90 | ??????/ ??????/ | ?????/ ?????/ | ?????/ ?????/ |
| ??DW-2 | 333/1 adds 373/4 | ????/ | ??＞14.60 | ??＞14.70 | ??????/ | ?????/ | ?????/ |
| ??DW-3 | 333/8 or 373/2 | ??≥19.6 | ??≥19.6 | ??≥17.64 | ????7.64 | ?????/ | ?????/ |
| ??DW-4 | 333/2 or 373/1 | ????/ | ??≥14.82 | ??≥9.8 | ??????/ | ?????/ | ?????/ |
| ??NHJ-44 | Hot setting | ????/ | ??＞19.6 | ??＞39.2 | ??????/ | ?????/ | ?????/ |
| ??HY912 | ????373/4 | ????/ | ????15.09 ????(83K) | ????21.27 | ????4.61 ????(323K) | ?????/ | ?????/ |
| ??672 | ????423/6 | ????/ | ????19.6 | ????14.7 | ??????/ | ?????/ | ????10.78 ????(423K) |
| ??H-006 | ????353/5 | ????/ | ????18.72～ ????19.31 | ????19.99～ ????23.62 | ??????/ | ?????/ | ????13.70 ???-13.92 ????(473K) |
By table as seen, tackiness agent of the present invention also has good shearing resistance at low temperature, very low temperature even at middle gentle high temperature, and stable performance, and the preparation method is simple, and raw material is easy to get.And the many no complete cutting performance data of existing tackiness agent, middle high-temperature behavior is not so good as the good of tackiness agent of the present invention more.Use technology shortcoming: DW-1, DW-2 and DW-4 ultra-low temperature glue also to be arranged, not anti-middle temperature to damp and hot sensitivity; DW-3 glue hot strength is poor, and used 590 solidifying agent zero pour are 20 ℃, the black thickness, and easily moisture absorption whiting was usually lost efficacy in some months; 672 adhesive curing temperature height need heat fused during use, solidifying agent is a solid, use inconvenient; Contain the aluminium powder filler in the HY912 glue component, thermal conductivity can increase in the use; The raw material of H-006 glue is not easy to obtain, the work complexity that is mixed during use, and solidifying agent is a solid, uses also inconvenient; NHJ-44 glue is moisture-proof warm not, and aging resistance is relatively poor, uses complex process.Above-mentioned existing tackiness agent is equal phase structure.
Embodiment 4
The tackiness agent that example 1 is made is cast into sheet material, is processed into standard specimen, measures its flexural strength and shock strength under differing temps, and it the results are shown in Table 2.
Table 2
| Condition of cure | Measure temperature (K) | Flexural strength (MPa) | Shock strength (MPa) |
| 100 ℃ 4 hours | ????77 ????300 | ????159.90 ????86.90 | ????19.22 ????14.21 |
| 160 ℃ hours | ????77 ????300 | ????145.68 ????9611.3 | ????16.31 ????12.20 |
Solidifying agent of the present invention can generate two phase structure with Resins, epoxy and toughner, makes adhesive system have higher second-order transition temperature, can use at very low temperature, be easy to preserve, be liquid, stable performance, can the moisture absorption rotten, but prolonged preservation never degenerate, the usage period is more than 3 years.
Tackiness agent of the present invention can obtain to have the two phase structure of toughness characteristics, overcome prior art low temperature adhesive thermal characteristics decline problem too far, solve rubber toughened system again and be unsuitable for the problem that low temperature environment uses, also overcome shortcomings such as many rings Resins, epoxy cost height, complex process, and mechanical property is good, at low temperature to mesophilic range, insensitive to temperature variation, cold-resistant thermal shocking, low toxicity also can be selected suitable prescription according to different needs.
Claims (12)
1. a low temperature adhesive is characterized in that being made up of the Resins, epoxy of (by weight) 100 parts, 14～150 parts varies solidifying agent, 0～3 part coupling agent and 5～35 parts toughner.
2. low temperature adhesive according to claim 1 is characterized in that said Resins, epoxy contains the bisphenol A epoxide resin of 0～100 heavy % and the ethylene oxidic ester epoxy resin of 0～100 heavy %.
3. low temperature adhesive according to claim 1, the oxirane value that it is characterized in that said Resins, epoxy is 0.3～1.0.
4. low temperature adhesive according to claim 1 is characterized in that the reactive hydrogen number of said varies is preferably 2～6.
5. low temperature adhesive according to claim 1 is characterized in that said coupling agent is a siloxane compound, can contain the amino or end epoxy group(ing) of end.
6. low temperature adhesive according to claim 1 is characterized in that said toughner is the liquid oligomer that contains urethane, polyester and polyether segment.
7. a varies solidifying agent that is used for low temperature adhesive is characterized in that by the amine condensation of 20～100 heavy %, the aromatic amine of 0～80 heavy %, the polymeric amide of 0～60 heavy % and the solidifying agent that 0～8 tertiary amine that weighs % is formed.
8. varies solidifying agent according to claim 4 is characterized in that said amine condensation contains to be connected in aromatic ring or/and primary amino on the aliphatic chain and/or secondary amino group that wherein aromatic ring can have 1～4.
9. varies solidifying agent according to claim 4 is characterized in that said amine condensation is the condenses of aminated compounds or the condenses of aminated compounds and ether compound, and said ether compound contains aromatic ring and aliphatic chain.
10. varies solidifying agent according to claim 4 is characterized in that said aromatic amine contains 1～4 aromatic ring.
11. varies solidifying agent according to claim 4, the amine value that it is characterized in that said polymeric amide is 200～400.
12. varies solidifying agent according to claim 4 is characterized in that nitrogen-atoms is connected on the aliphatic chain in the said tertiary amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97104098 CN1197098A (en) | 1997-04-24 | 1997-04-24 | Low temp. adhesive and firming agent used for low temp. adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97104098 CN1197098A (en) | 1997-04-24 | 1997-04-24 | Low temp. adhesive and firming agent used for low temp. adhesive |
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| Publication Number | Publication Date |
|---|---|
| CN1197098A true CN1197098A (en) | 1998-10-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97104098 Pending CN1197098A (en) | 1997-04-24 | 1997-04-24 | Low temp. adhesive and firming agent used for low temp. adhesive |
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| CN (1) | CN1197098A (en) |
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|---|---|---|---|---|
| CN100335574C (en) * | 2003-02-21 | 2007-09-05 | 中国科学院等离子体物理研究所 | High-strength epoxy impregnating varnish used at extremely low temperature and preparation method and use method thereof |
| WO2010097051A1 (en) * | 2009-02-27 | 2010-09-02 | 汉高（中国）投资有限公司 | Room-temperature curable epoxy structural adhesive composition and preparation method thereof |
| CN101942287A (en) * | 2010-09-27 | 2011-01-12 | 彩虹集团公司 | Low-temperature electricity conducting glue and preparation method thereof |
| CN101210162B (en) * | 2006-12-28 | 2011-11-30 | 西安西电变压器有限责任公司 | Semi-conductor adhesive and preparation method thereof |
| CN101679579B (en) * | 2007-06-20 | 2012-05-30 | 陶氏环球技术公司 | Crash durable epoxy adhesives with very low sensitivity to temperature variations |
| CN102504742A (en) * | 2011-11-02 | 2012-06-20 | 核工业理化工程研究院 | Bonding glue quickly solidified at room temperature |
| US8426986B2 (en) | 2008-11-21 | 2013-04-23 | Henkel Corporation | Phase separated curable compositions |
| CN103374319A (en) * | 2013-04-26 | 2013-10-30 | 中国科学院上海技术物理研究所 | Modified low-temperature structural adhesive and preparation method thereof |
| CN104559893A (en) * | 2015-01-27 | 2015-04-29 | 航天材料及工艺研究所 | Low-temperature epoxy resin adhesive and application thereof |
| CN106479417A (en) * | 2016-11-08 | 2017-03-08 | 深圳市宝力新材料有限公司 | LED packaging plastic and preparation method thereof |
| CN111808563A (en) * | 2020-07-31 | 2020-10-23 | 哈尔滨玻璃钢研究院有限公司 | Multifunctional heat-resistant high-performance adhesive and preparation method and application thereof |
| CN114106658A (en) * | 2021-12-21 | 2022-03-01 | 安徽省金盾涂料有限责任公司 | Environment-friendly ship drinking water tank paint |
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1997
- 1997-04-24 CN CN 97104098 patent/CN1197098A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335574C (en) * | 2003-02-21 | 2007-09-05 | 中国科学院等离子体物理研究所 | High-strength epoxy impregnating varnish used at extremely low temperature and preparation method and use method thereof |
| CN101210162B (en) * | 2006-12-28 | 2011-11-30 | 西安西电变压器有限责任公司 | Semi-conductor adhesive and preparation method thereof |
| CN101679579B (en) * | 2007-06-20 | 2012-05-30 | 陶氏环球技术公司 | Crash durable epoxy adhesives with very low sensitivity to temperature variations |
| US8426986B2 (en) | 2008-11-21 | 2013-04-23 | Henkel Corporation | Phase separated curable compositions |
| WO2010097051A1 (en) * | 2009-02-27 | 2010-09-02 | 汉高（中国）投资有限公司 | Room-temperature curable epoxy structural adhesive composition and preparation method thereof |
| CN101942287A (en) * | 2010-09-27 | 2011-01-12 | 彩虹集团公司 | Low-temperature electricity conducting glue and preparation method thereof |
| CN102504742A (en) * | 2011-11-02 | 2012-06-20 | 核工业理化工程研究院 | Bonding glue quickly solidified at room temperature |
| CN103374319A (en) * | 2013-04-26 | 2013-10-30 | 中国科学院上海技术物理研究所 | Modified low-temperature structural adhesive and preparation method thereof |
| CN104559893A (en) * | 2015-01-27 | 2015-04-29 | 航天材料及工艺研究所 | Low-temperature epoxy resin adhesive and application thereof |
| CN106479417A (en) * | 2016-11-08 | 2017-03-08 | 深圳市宝力新材料有限公司 | LED packaging plastic and preparation method thereof |
| CN111808563A (en) * | 2020-07-31 | 2020-10-23 | 哈尔滨玻璃钢研究院有限公司 | Multifunctional heat-resistant high-performance adhesive and preparation method and application thereof |
| CN111808563B (en) * | 2020-07-31 | 2022-05-17 | 哈尔滨玻璃钢研究院有限公司 | Multifunctional heat-resistant high-performance adhesive and preparation method and application thereof |
| CN114106658A (en) * | 2021-12-21 | 2022-03-01 | 安徽省金盾涂料有限责任公司 | Environment-friendly ship drinking water tank paint |
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