CN105199081B - It is a kind of for the curing agent of epoxy resin and used at ultra-low temperature epoxy adhesive - Google Patents
It is a kind of for the curing agent of epoxy resin and used at ultra-low temperature epoxy adhesive Download PDFInfo
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- CN105199081B CN105199081B CN201510775886.1A CN201510775886A CN105199081B CN 105199081 B CN105199081 B CN 105199081B CN 201510775886 A CN201510775886 A CN 201510775886A CN 105199081 B CN105199081 B CN 105199081B
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Abstract
The used at ultra-low temperature epoxy adhesive prepared the present invention relates to a kind of curing agent for epoxy resin and with the curing agent；Curing agent is a kind of open loop deamination generation as obtained by 201 compound aliphatic cyclic amines of FZ and thiocarbamide are condensed under diglycol effectOligomer.Wherein, 201 compound aliphatic cyclic amines of FZ are methyl cyclohexane diamines, methyl ring pentanediamine and N aminoethyl piperazines, and the weight of 201 compound aliphatic cyclic amines of FZ, thiocarbamide and diglycol is 100:25:20, it is 95 that used at ultra-low temperature epoxy adhesive, which includes weight,:15 35 epoxy resin and the curing agent；Epoxy resin is the bisphenol A-type tetraglycidel ether epoxy resin E 51 of bifunctionality；The present invention, which uses, to be containedOpen loop aliphatic cyclic amine make curing agent, not only containing amido but also contained in molecular structure
Description
Technical field
The present invention relates to a kind of curing agent and a kind of epoxy resin adhesive, more particularly to a kind of consolidating for epoxy resin
Agent and the used at ultra-low temperature epoxy adhesive prepared with the curing agent.
Background technology
Matrix resin of the epoxy resin as high-performance composite materials, because with good mechanical property, adhesion strength is high,
The electrical insulation capability that shrinking percentage is low, stability is good, excellent, good processing performance etc. and in machinery, electronics, aerospace, ship
It is widely used in the fields such as oceangoing ship Industry and Construction.
In epoxy resin application process, curing agent occupies highly important status.Epoxy curing agent is various in style,
For low form curing agent generally using aliphatic polyamine class curing agent, toxicity is larger, strong to human skin irritation at present, such
When curing agent is reacted with epoxy resin, system thermal discharge is big, and working life is short and the flexible difference of solidfied material, when storing in air, Gu
Change product there is also frosting or the phenomenon that hazes, this is because the carbon dioxide/steam stored in primary amine group and air occurs
Caused by carbaminate caused by reaction.And currently as cryogenic curing agent using it is more be polymercaptan and polyamines
With the addition product of thiocarbamide, polymercaptan and tertiary amine, which are combined together, can obtain -20 DEG C~0 DEG C cured cryogenic curing agent, but
Polymercaptan is thick at room temperature, and viscosity is very big, and the smell is awful, and toxicity is big, therefore does not select polymercaptan serial.
Invention content
The object of the present invention is to provide a kind of epoxy curing agents for ultralow temperature, have the following advantages：First, by
Primary amine in aliphatic cyclic amine is condensed addition with thiocarbamide, overcomes aliphatic polyamine cured product and hazes or the phenomenon that frosting；Second,
The preparation process of curing agent is simple, only need to mix the compound aliphatic cyclic amines of FZ-201 in diglycol medium with thiocarbamide, in
60-135 DEG C of reaction 2h is to get to required curing agent；Third, the curing agent make adhesive processing performance improve on a large scale,
The curing agent is the liquid of low viscosity at normal temperatures, simple with epoxy resin hybrid technique, and can be sufficiently mixed uniformly；The
Four, it can cure at low temperature, it might even be possible to cure under -15 DEG C of ultralow temperature, greatly reduce solidification temperature range so that
The cryogenic curing of epoxy resin is carried out, and has very important meaning for the construction structure glue under low temperature；5th, it is added
Comprising rigid phenyl ring segment in modifying agent, solidfied material mechanical strength is big or even remains to keep sizable strong under ultralow temperature
Degree, also with certain high-temperature behavior；6th, it is raw materials used both from commercially available product, it is cheap and easy to get；7th, use the curing
The Ultralow-temperatureepoxy epoxy adhesive that agent is prepared, intensity is big, and gel time and first time admittedly are short, and preparation process is simple, at low cost.
Technical scheme is as follows：
It is in a contracting diethyl by the compound aliphatic cyclic amines of FZ-201 and thiocarbamide provided by the present invention for the curing agent of epoxy resin
A kind of deamination generation obtained by being condensed under glycol facilitationOligomer, wherein, the compound alicyclic rings of FZ-201
The weight of amine, the thiocarbamide and the diglycol is 100:25:20.
The compound aliphatic cyclic amines of the FZ-201 are methyl cyclohexane diamines, methyl ring pentanediamine and N- aminoethyl piperazines.
The epoxy resin be aromatic glycidyl ether epoxy resin, the aromatic glycidyl ether epoxy resin
For the bisphenol A-type tetraglycidel ether epoxy resin of bifunctionality, model E-51.
Used at ultra-low temperature epoxy adhesive provided by the invention, including epoxy resin and curing agent；The epoxy resin and solid
The weight of agent is 95:5-50.
The curing agent is obtained to be condensed under diglycol facilitation by the compound aliphatic cyclic amines of FZ-201 and thiocarbamide
A kind of deamination generationOligomer, wherein, the compound aliphatic cyclic amine of the FZ-201, the thiocarbamide and a contracting
The weight of diethylene glycol is 100:25:20.
The epoxy resin is bisphenol A-type tetraglycidel ether epoxy resin, and model E-51, epoxide number is
0.48-0.54(100g/g)。
Used at ultra-low temperature epoxy adhesive provided by the invention, further includes coupling agent；The epoxy resin, curing agent and coupling
The weight of agent is 95: 5-50:1-10；When the weight of the epoxy resin, curing agent and coupling agent is 95:
15-35:It is better during 1-4.The coupling agent is γ aminopropyltriethoxy silane.
Used at ultra-low temperature epoxy adhesive provided by the invention, still further comprises modifying agent；The epoxy resin, curing
The weight of agent, coupling agent and modifying agent is 95:5-50:1-10：188-208.
The modifying agent increases for the flexibility containing epoxy group, the BE of end carboxyl group and unsaturated double-bond and polyamide
Tough dose, the accelerating agent containing 2,4,6- tri- (dimethylamino methyl) phenol, silicon powder filler is low with what it is containing benzyl glycidyl ether to be glued
Spend the mixture of diluent composition.
Cryogenic curing agent according to the present invention is the addition product of compound aliphatic cyclic amine and thiocarbamide, compound aliphatic cyclic amine and thiocarbamide
Deamination reaction is carried out, generation has the polyamines of thiourea bond in the molecule, and structural formula is as follows：
Wherein R1, R2The segment of respectively methyl cyclohexyl diamine, methyl ring pentanediamine or N- aminoethyl piperazines.
Cure the thiocarbamide in agent molecule with keto-acid and enol form equilibrium state to exist, this enol form compound and mercapto one
Sample and epoxy reaction play special fast solidity.Its reaction process with epoxy resin is as follows：
At room temperature, the expression activitiy that mercapto is individually reacted with epoxy resin is low, but when having the amine to make accelerating agent, can be with shape
Into mercaptan ion, curing reaction is carried out with the rate of several times polyamine, can more be shown in low-temperature setting.
Tertiary amine can also form epoxy anion with epoxy reaction, and the anion and mercapto carry out necleophilic reaction.
Wherein, R is the segment of N- aminoethyl piperazines.
The cured product of epoxy resin and curing agent reaction generation space network.The adduct of aliphatic cyclic amine and thiocarbamide,
In addition to amino can with other than epoxy reaction, also mercapto also can increase solidification temperature range with epoxy reaction, can be low
Cured under temperature, meanwhile, the molecular mass increase between crosslinking points, crosslink density reduces, and brittleness is caused to reduce and improved.
The present invention has such as the curing agent of epoxy resin and with the used at ultra-low temperature epoxy adhesive that this curing agent is prepared
Lower advantage：
The present invention is modified the compound aliphatic cyclic amines of FZ-201 using thiocarbamide and makees curing agent, not only amino-contained but also has contained in molecule, thus ring of the crosslink density of the epoxy resin adhesive of curing agent solidification than containing only aliphatic cyclic amine curing agent solidification
The crosslink density of oxygen resin cured matter is low, overcomes the epoxy resin cured product of the aliphatic cyclic amine curing agent solidification of the latter's only amino-contained
The shortcomings that brittleness is big, irritation is small, small toxicity, and the epoxy resin adhesive prepared with the curing agent of the present invention is in ultra-low temperature surroundings
Under still have sizable intensity, suitable for being used under ultra-low temperature surroundings.
In addition, also have preparation process it is simple, only need to by the compound aliphatic cyclic amines of FZ-201 directly with thiocarbamide in a contracting diethyl two
It is mixed in alcohol medium, reacts 2h in 60-135 DEG C, you can obtain curing agent according to the present invention；Use the curing agent of the present invention
Prepared epoxy adhesive, can make the processing performance of adhesive improve on a large scale；The curing agent is low-viscosity (mobile) liquid under room temperature,
It is simple with epoxy resin hybrid technique, and can be sufficiently mixed uniformly；The epoxy resin adhesive of the present invention can be at low temperature
Curing, it might even be possible to cure under -15 DEG C of ultralow temperature, greatly reduce solidification temperature range so that epoxy resin it is ultralow
Temperature curing is carried out, and has very important meaning for the construction structure glue under low temperature；The epoxy resin adhesive of the present invention
Also further containing modifying agent, solidfied material mechanical strength is big or even remains to keep sizable mechanical strength under ultralow temperature,
Due to containing rigid phenyl ring in modifying agent, and it is that solidfied material maintains certain high-temperature behavior；It is raw materials used to be all from commercially available product,
It is cheap and easy to get；The Ultralow-temperatureepoxy epoxy adhesive prepared using the curing agent, gel time and first time admittedly are short, preparation process letter
It is single, it is at low cost.
Specific embodiment
The technology of preparing of the present invention is further described below in conjunction with specific embodiment, lists the following example and ratio
Compared with example, in order that the present invention is explained in more detail, but patent of the present invention is not limited only to these embodiments.
The preparation of cryogenic curing agent：
Into the reactor with blender, condenser, 100g FZ-201 compound fats amine, 25g thiocarbamides and 20g are added in
Diglycol is uniformly mixed in 60 DEG C, then is to slowly warm up to 135 DEG C, is kept the temperature 2h, is gradually being cooled to room temperature, is going out
Material is to get to the cryogenic curing agent of yellow green low viscosity lime-preserved egg taste.
The preparation embodiment of used at ultra-low temperature epoxy resin steel bonding glue：
Embodiment（1）
Weigh 95g bisphenol A type epoxy resins E-51（Epoxide number 0.48-0.54）, 5g benzyl glycidyl ethers, 120g silicon is micro-
Powder, as component A；
Weigh 15g cryogenic curing agent, 35g polyamide, 2g 2,4,6- tri- (dimethylamino methyl) phenol, 2g gamma-aminos
Propyl-triethoxysilicane, BEs of the 8g containing epoxy group, end carboxyl group and unsaturated double-bond, 158g silicon powders, as component
B。
A and two components of B are individually placed to freeze 2 hours under 0~-5 DEG C of low temperature, then by A and B by weight ratio 1:1 is mixed
It closes uniform, is by viscous material using No. 45 steel discs, prepares steel disc by GB7124-86 standards and shear sample, marked by GB/T699-1999
Standard prepares tensile test piece, prepares hardness test sample by GB531-83 standards, sample is placed in -15 DEG C of refrigerator,
Gel time is recorded simultaneously and is just consolidated the time, every mechanical property is tested after 10 days, and test result is listed in table 1.
Embodiment（2）
Weigh 95g bisphenol A type epoxy resins E-51（Epoxide number 0.48-0.54）, 5g benzyl glycidyl ethers, 120g silicon is micro-
Powder, as component A；
Weigh 25g cryogenic curing agent, 25g polyamide, 2g 2,4,6- tri- (dimethylamino methyl) phenol, 2g gamma-aminos
Propyl-triethoxysilicane, BEs of the 8g containing epoxy group, end carboxyl group and unsaturated double-bond, 158g silicon powders, as component
B。
A and two components of B are individually placed to freeze 2 hours under 0~-5 DEG C of low temperature, then by A and B by weight ratio 1:1 is mixed
It closes uniform, is by viscous material using No. 45 steel discs, prepares steel disc by GB7124-86 standards and shear sample, marked by GB/T699-1999
Standard prepares tensile test piece, prepares hardness test sample by GB531-83 standards, sample is placed in -15 DEG C of refrigerator,
Gel time is recorded simultaneously and is just consolidated the time, every mechanical property is tested after 10 days, and test result is listed in table 1.
Embodiment（3）
Weigh 95g bisphenol A type epoxy resins E-51（Epoxide number 0.48-0.54）, 5g benzyl glycidyl ethers, 120g silicon is micro-
Powder, as component A；
Weigh 35g cryogenic curing agent, 15g polyamide, 2g 2,4,6- tri- (dimethylamino methyl) phenol, 2g gamma-aminos
Propyl-triethoxysilicane, BEs of the 8g containing epoxy group, end carboxyl group and unsaturated double-bond, 158g silicon powders, as component
B。
A and two components of B are individually placed to freeze 2 hours under 0~-5 DEG C of low temperature, then by A and B by weight ratio 1:1 is mixed
It closes uniform, is by viscous material using No. 45 steel discs, prepares steel disc by GB7124-86 standards and shear sample, marked by GB/T699-1999
Standard prepares tensile test piece, prepares hardness test sample by GB531-83 standards, sample is placed in -15 DEG C of refrigerator,
Gel time is recorded simultaneously and is just consolidated the time, every mechanical property is tested after 10 days, and test result is listed in table 1.
The properties of used at ultra-low temperature epoxy adhesive prepared by 1. embodiment 1-3 of table
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Shear strength (MPa) | 5.36 | 9.20 | 14.12 |
| Tensile strength (MPa) | 15.7 | 17.16 | 19.39 |
| Hardness (HD) | Curing is incomplete | 55 | 68 |
| Gel time (min) | 65 | 43 | 33 |
| Just consolidate the time (min) | 77 | 52 | 38 |
By being can be seen that the comparison of parameter in A, two composition weight numbers of B, ratio, solidification temperature all same situation
Under, cryogenic curing agent and polyamide ratio are bigger, and curing situation is better, and intensity is bigger, and gel time and first time admittedly are shorter,
And properties can meet the standard of construction structure glue under ultralow temperature.
Claims (3)
1. a kind of used at ultra-low temperature epoxy adhesive, it is characterised in that：Including epoxy resin and curing agent；The curing agent is served as reasons
A kind of deamination generation obtained by being condensed under diglycol facilitation of the compound aliphatic cyclic amines of FZ-201 and thiocarbamideOligomer, R1 , R2 Respectively methyl cyclohexyl diamine, methyl ring pentanediamine or N- ammonia second
The segment of base piperazine, wherein, the parts by weight of the compound aliphatic cyclic amine of the FZ-201, the thiocarbamide and the diglycol are matched
Than being 100:25:20；The epoxy resin is the bisphenol-A type epoxy resin E-51 of bifunctionality, and epoxide number is
0.48-0.54(100g/g)；Coupling agent is further included, the coupling agent is γ-aminopropyltriethoxywerene werene；It further includes and changes
Property agent, the modifying agent for containing epoxy group, the BE of end carboxyl group and unsaturated double-bond and polyamide flexibility increase
Tough dose, the accelerating agent containing 2,4,6- tri- (dimethylamino methyl) phenol, silicon powder filler is with containing benzyl glycidyl ether
Low viscosity diluent composition mixture；The epoxy resin, curing agent, coupling agent and modifying agent weight be
95:15-35:1-10：188-208 .
2. used at ultra-low temperature epoxy adhesive as described in claim 1, which is characterized in that the compound aliphatic cyclic amines of the FZ-201
For methyl cyclohexane diamines, methyl ring pentanediamine and N- aminoethyl piperazines.
3. used at ultra-low temperature epoxy adhesive as described in claim 1, which is characterized in that the epoxy resin, curing agent and idol
The weight for joining agent is 95:15-35:1-4.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510775886.1A CN105199081B (en) | 2015-11-13 | 2015-11-13 | It is a kind of for the curing agent of epoxy resin and used at ultra-low temperature epoxy adhesive |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510775886.1A CN105199081B (en) | 2015-11-13 | 2015-11-13 | It is a kind of for the curing agent of epoxy resin and used at ultra-low temperature epoxy adhesive |
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| CN105199081B true CN105199081B (en) | 2018-06-29 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105533828B (en) * | 2016-01-26 | 2017-09-01 | 广东宏杰内衣实业有限公司 | A kind of seamless synthetism T-shirt |
| CN105835080A (en) * | 2016-01-27 | 2016-08-10 | 宁波新大陆磁制品有限公司 | Attraction piece |
| CN106146802B (en) * | 2016-08-19 | 2019-05-03 | 武汉工程大学 | Application of two (the methyl mercapto) -4- amino toluene of compound 2- ghiourea group -3,5- in epoxy-resin systems |
| CN113549417B (en) * | 2021-07-19 | 2023-04-14 | 广东恒大新材料科技有限公司 | Fast-curing high-strength epoxy adhesive |
| CN114163614B (en) * | 2021-11-22 | 2024-05-14 | 瑞奇(广东)技术有限公司 | Epoxy curing agent and preparation method and application thereof |
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| CN102604044A (en) * | 2012-02-28 | 2012-07-25 | 武汉工程大学 | Thiourea modified low temperature curing agent and preparation method thereof |
| CN103980463A (en) * | 2014-04-23 | 2014-08-13 | 中科院广州化学有限公司南雄材料生产基地 | Epoxy resin solvent-free low temperature curing agent, preparation method and application thereof |
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2015
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| US5444127A (en) * | 1992-10-19 | 1995-08-22 | Henkel Corporation | Tertiary amine derivatives as components of polymer forming systems |
| CN102604044A (en) * | 2012-02-28 | 2012-07-25 | 武汉工程大学 | Thiourea modified low temperature curing agent and preparation method thereof |
| CN103980463A (en) * | 2014-04-23 | 2014-08-13 | 中科院广州化学有限公司南雄材料生产基地 | Epoxy resin solvent-free low temperature curing agent, preparation method and application thereof |
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Address after: 433000 Hubei national high tech Zone, new material industrial park, Xianhe Road, No. 1 Applicant after: Hubei green home materials technology Limited by Share Ltd Address before: 60 No. 433000 Hubei province Xiantao Xiantao office Sha Tsui Road Applicant before: HUBEI GREENHOME FINE CHEMICAL CO., LTD. |
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