CN110157368A - Adhesive and electrochemical device using same - Google Patents
Adhesive and electrochemical device using same Download PDFInfo
- Publication number
- CN110157368A CN110157368A CN201810149723.6A CN201810149723A CN110157368A CN 110157368 A CN110157368 A CN 110157368A CN 201810149723 A CN201810149723 A CN 201810149723A CN 110157368 A CN110157368 A CN 110157368A
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- China
- Prior art keywords
- adhesive
- epoxy resin
- hyperbranched polyorganosiloxane
- epoxy
- weight ratio
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to an adhesive and a device using the same. The adhesive mainly contains epoxy resin, and also contains hyperbranched polysiloxane with epoxy functional groups, wherein the weight ratio of the epoxy resin to the hyperbranched polysiloxane in the adhesive is 100 (5-30). According to the adhesive, the hyperbranched polysiloxane with the epoxy functional group is introduced into the epoxy resin structural adhesive, so that the modifier for improving the fatigue resistance of the epoxy resin can be used on the premise of basically not losing the viscosity of the epoxy resin, and the effect of improving the bonding reliability between the epoxy resin structural adhesive and a metal insert is finally achieved.
Description
Technical field
The present invention relates to chemical fields, specifically, are related to a kind of adhesive and the electrochemical appliance of the adhesive.
Background technique
Electric car is following development trend as a kind of novel environment friendly automobile.But all the time, electric car is just
It is limited by cost and the technical bottlenecks such as mileage is short.Along with the progress of science and technology, the component of electric car most critical, power battery box
Body also obtains technical innovation.It is multiple from the fiber-reinforced resin base of the power battery cabinet based on aluminium alloy till now
Condensation material cabinet, capacity, service life and the cost of battery are all optimized constantly.However, when fibrous composite is replaced
After hardware, Battery case is in the hole in use in order to prevent, is used for power battery cabinet key portion
The finally new technical requirements of the adhesive faec of its structural bond function of part such as have resin composite materials and metal base high
Adhesive strength, processability are adjustable, resistance to long-term high/low temperature and damp and hot impact, resisting salt fog corrosion, excellent steam permeation barrier, with
And Fatigue Vibration repeatedly under long-term operating condition form etc..
For the structural bond in power battery cabinet between fibre reinforced composites and metal insert, acrylate and
Epoxy resin tackifier is preferred.However, since, containing the structural unit of facile hydrolysis, esters of acrylic acid adhesive is often in structure
Have the defects that not moisture-resistant heat ageing, and it is too high to the cost of the acrylate adhesive of modified humidity resistance；Relative to
Tradition or modified form esters of acrylic acid adhesive, the moisture-resistant hot property of epoxy resin is then very excellent, but its resistance is drawn repeatedly
The fatigue behaviour of stress or shear stress is then very insufficient, needs to develop a kind of epoxy resin knot with excellent fatigue resistance energy
Structure glue.In order to improve the anti-fatigue performance of epoxy resin, using the polymer such as rubber or organosilicon as toughener, with inorganic filler
The anti-fatigue performance for acting synergistically to improve epoxy resin as reinforcement drug is the widely used means of current industry.With tradition
Unlike glue point, power battery cabinet glue position is in addition to requiring adhesive to have high adhesive strength, resistance to long-term height
Fatigue Vibration repeatedly under mild damp and hot impact, resisting salt fog corrosion, excellent steam permeation barrier, and long-term operating condition form
Etc. except performances, should also have excellent mobility.However, prior art preparation fatigue resistance epoxyn often by
A large amount of polymer toughener and filler are added in system and causes system viscosity very big, are not suitable for power battery cabinet
Glue position is used a bit.
Summary of the invention
In consideration of it, first aspect present invention provides a kind of adhesive, above-mentioned at least one can be effectively solved the problems, such as.
A kind of adhesive, mainly contains epoxy resin, and the adhesive also contains with the hyperbranched of epoxy-functional
Polysiloxanes, wherein the weight ratio of epoxy resin described in the adhesive and the hyperbranched polyorganosiloxane is 100:5~30.
Second aspect of the present invention provides a kind of device comprising fibre reinforced composites element and hardware, it is described
Fibre reinforced composites element and the hardware are combined as a whole by above-mentioned adhesive.
The present invention at least have it is below the utility model has the advantages that
(1) adhesive in epoxy resin structural adhesive by introducing the hyperbranched poly silicon oxygen with epoxy-functional
Alkane, the modifying agent of epoxy resin anti-fatigue performance can be improved, and final under the premise of not losing epoxy resin viscosity substantially by leading to
Achieve the effect that improve it to bonding reliability between composite material and metal insert in lithium-ion power battery box.
(2) adhesive uses the novel coordination plasticizing system by hyperbranched polyorganosiloxane group, assigns it to ensure that
High adhesive strength, resistance to long-term high/low temperature and damp and hot impact, resisting salt fog corrosion, excellent are all had with metal and fibrous composite
The advantages that Fatigue Vibration repeatedly under processability, and long-term operating condition form.
(3) by introducing the hyperbranched polyorganosiloxane with low viscosity and impact modification and traditional epoxy resin and rigid
Property particle form collaboration system, thus can not only meet lithium ion battery case to adhesive strength, wet-heat resisting, anti-high and low-temp recycle
Fatigue impact under impact, and long-term operating condition form, and can satisfy certain special power battery cabinet designs to gluing
The requirement for the excellent processability that agent proposes.
Specific embodiment
Further illustrate that the present invention, these embodiments are only intended to illustrate the present invention below by embodiment and comparative example,
The present invention is not limited to following embodiments.All modifying or equivalently replacing the technical solution of the present invention, without departing from this hair
The spirit and scope of bright technical solution should all cover within the protection scope of the present invention.The purpose of the present invention is to provide one kind
Adhesive and the electrochemical appliance for using the adhesive.
Illustrate adhesive according to a first aspect of the present invention first.
The adhesive, mainly contains epoxy resin, and the adhesive also contains with the hyperbranched of epoxy-functional
Polysiloxanes, wherein the weight ratio of epoxy resin described in the adhesive and the hyperbranched polyorganosiloxane be 100:(5~
30)。
Adhesive of the present invention in epoxy resin structural adhesive by introducing the hyperbranched poly with epoxy-functional
Siloxanes, the modifying agent of epoxy resin anti-fatigue performance can be improved under the premise of not losing epoxy resin viscosity substantially by leading to, and
Be finally reached improve its in lithium-ion power battery box between composite material and metal insert bonding reliability effect.Due to
The difference of epoxy resin-base, hyperbranched polyorganosiloxane and epoxy resin containing epoxy have better compatibility.Due to poly- silicon
The silicon oxygen crystallinity of oxygen alkane and high free volume cause it to have high impact modified effect to epoxy resin.
Adhesive according to a first aspect of the present invention, the epoxy resin are bisphenol A type epoxy resin or alicyclic epoxy
Resin.
Adhesive according to a first aspect of the present invention, the hyperbranched polyorganosiloxane with epoxy-functional are with KH-
The hyperbranched polyorganosiloxane of 560 synthesis.
Adhesive according to a first aspect of the present invention, the adhesive further contains filler, described in the adhesive
The weight ratio of epoxy resin, the hyperbranched polyorganosiloxane and the filler is 100:(5~30): (1~100).The filler
Preferably fumed silica, talcum powder, clay or calcite.
The present invention is by introducing the hyperbranched polyorganosiloxane with low viscosity and impact modification and traditional epoxy resin
Collaboration system is formed with rigid particles, so that lithium ion battery case can not only be met to adhesive strength, wet-heat resisting, anti-high and low-temp
Fatigue impact under circulation impact, and long-term operating condition form, and can satisfy certain special power battery cabinet designs pair
The requirement for the excellent processability that adhesive proposes.
Adhesive according to a first aspect of the present invention, the adhesive further contain toughener, wherein the adhesive
Described in epoxy resin, the hyperbranched polyorganosiloxane and the toughener weight ratio be 100:(5~30): (5~50),
The toughener is response type toughener, preferably polysulfide rubber, carboxylated nitrile rubber or epoxy organosilicon polymer.
Adhesive according to a first aspect of the present invention, the adhesive further contain amine curing agent, wherein the glue
The weight ratio of epoxy resin described in stick, the hyperbranched polyorganosiloxane and the amine curing agent is 100:(5~30):
(2~50), the amine curing agent are aliphatic polyamine organic matter, preferably hexamethylene diamine, polyethylene polyamine or by two
The curing agent of ketone acrylamide and diethylenetriamines addition.
Adhesive according to a first aspect of the present invention, the adhesive further contain curing accelerator, wherein the glue
The weight of epoxy resin described in stick, the hyperbranched polyorganosiloxane and described 2,4,6- tri- (dimethylamino methyl) phenol
Than for 100:(5~30): (0.1~1), the curing accelerator are tertiary amine organic matter, preferably 2,4,6- tri- (dimethylamino first
Base) phenol.The curing accelerator can promote reacting for amine curing agent and epoxy resin.
Adhesive according to a first aspect of the present invention, the adhesive is for viscose fibre enhancing composite material and metal.
The adhesive can effectively improve be bonded between fibre reinforced composites and metal insert in lithium-ion-power cell it is reliable
Property.
Adhesive of the invention uses the novel coordination plasticizing system by hyperbranched polyorganosiloxane group, to ensure that tax
Give its all have with metal and fibrous composite high adhesive strength, resistance to long-term high/low temperature and damp and hot impact, resisting salt fog corrosion,
The advantages that Fatigue Vibration repeatedly under excellent processability, and long-term operating condition form.
Following components is uniformly mixed by the preparation method of adhesive of the present invention by weight: 100 parts of epoxy resin,
1~100 part of 5~50 parts of 5-30 parts of hyperbranched polyorganosiloxane, toughener, filler, amine curing agent 2-50 containing epoxy-functional
Part and curing accelerator 0.1-1 parts.During mixing, it can keep being heated to certain temperature.
Device according to a second aspect of the present invention comprising fibre reinforced composites element and hardware, the fibre
Dimension enhancing composite component and the hardware are combined as a whole by above-mentioned adhesive.
Embodiment 1
(1) under agitation, by 45.00g γ-glycidyl ether oxygen propyl trimethoxy silicane, 5.15g deionized water
After three-necked flask is added with 0.09g tetramethylammonium hydroxide (20% aqueous solution), constant temperature flows back 2 hours at 40 DEG C, obtains molten
Liquid A；
(2) under agitation, 30.89g trim,ethylchlorosilane is dissolved in by obtaining solution B in 54.00mL methanol；
(3) under the conditions of stirring and nitrogen protection, solution B is poured into solution A at 60 DEG C, and constant temperature returns at 60 DEG C
Stream obtained crude product after 6 hours after vacuum distillation；
(4) after crude product being dissolved in methylene chloride, insoluble matter is filtered, to get to containing after being evaporated under reduced pressure, being dried in vacuo
Active function groups are the hyper-branched silicone resin containing epoxy-functional；
(5) by weight, by the over-expense containing epoxy-functional prepared by 100g bisphenol A type epoxy resin, 15g step 4)
SiClx resin, 5g polysulfide rubber, 2,4,6- tri- (dimethylamino methyl) phenol of 100g talcum powder, 50g hexamethylene diamine and 0.1g
It is uniformly mixed under the conditions of 90 DEG C of temperature to get high-performance epoxy resin sqtructural adhesive is arrived.
Embodiment 2
By weight, by official containing epoxy prepared by step (4) in 100g cycloaliphatic epoxy resin, 30g embodiment one
Hyper-branched silicone resin, 50g carboxylated nitrile rubber, 100g clay, 2g polyethylene polyamine and the 0.1g 2,4,6- tri- (two that can be rolled into a ball
Methyaminomethyl) phenol under the conditions of 90 DEG C of temperature be uniformly mixed to get arrive high-performance epoxy resin sqtructural adhesive.
Embodiment 3
By weight, by official containing epoxy prepared by step (4) in 100g bisphenol A type epoxy resin, 10g embodiment one
Hyper-branched silicone resin, 10g epoxy organosilicon polymer, 100g calcite, 20g aliphatic polyamine organic matter and the 0.1g that can be rolled into a ball
2,4,6- tri- (dimethylamino methyl) phenol are uniformly mixed to arrive high-performance epoxy resin structure under the conditions of 90 DEG C of temperature
Adhesive.
Embodiment 4
By weight, by official containing epoxy prepared by step (4) in 100g bisphenol A type epoxy resin, 10g embodiment one
Hyper-branched silicone resin, 15g carboxylated nitrile rubber, 30g calcite, 20g aliphatic polyamine organic matter and the 0.5g 2 that can be rolled into a ball,
4,6- tri- (dimethylamino methyl) phenol are uniformly mixed to arrive high-performance epoxy resin structure glue under the conditions of 90 DEG C of temperature
Stick.
Embodiment 5
By weight, by official containing epoxy prepared by step (4) in 100g bisphenol A type epoxy resin, 5g embodiment one
Hyper-branched silicone resin, 25g carboxylated nitrile rubber, 5g talcum powder, 20g aliphatic polyamine organic matter and the 1g 2,4 that can be rolled into a ball,
(dimethylamino methyl) phenol of 6- tri- is uniformly mixed to arrive high-performance epoxy resin structure gluing under the conditions of 90 DEG C of temperature
Agent.
Comparative example 1
By weight, by 2,4,6- tri- (dimethylamino of 100g bisphenol A type epoxy resin, 50g hexamethylene diamine and 0.1g
Methyl) phenol under the conditions of 90 DEG C of temperature be uniformly mixed to get to anhydride cured epoxy (without have it is epoxy functionalized
The hyperbranched polyorganosiloxane of group).
Comparative example 2
By weight, by 100g bisphenol A type epoxy resin, 20g polysulfide rubber, 50g hexamethylene diamine and 0.1g 2,4,6-
Three (dimethylamino methyl) phenol are uniformly mixed under the conditions of 90 DEG C of temperature and (are free of to get to anhydride cured epoxy
Hyperbranched polyorganosiloxane with epoxy-functional).
Using 8802 fatigue testers of Instron company, the U.S., under 40Hz, 23 degrees celsius, testing example
The adhesive fatigue performance of 1-5 and comparative example 1-2, specific test result is as follows shown in table.
Table one
Static breaking load presses 16MPa, and " > " indicates that all there is no destroying in these period exemplars
Table two
As can be seen from the above table, the adhesive exemplar of hyperbranched polyorganosiloxane is not added in comparative example 1, in 20% maximum
Under the action of static breaking load, exemplar does not damage after can keeping 1,000,000 fatigue and cyclics, but when load is promoted to 25% He
When 30%, exemplar is only able to maintain tens of thousands of times and does not damage.Different, after rubber and filler coordination plasticizing comparative example 2
Even if being loaded into 30% maximum static load with embodiment 1-5, exemplar is also able to maintain 3,000,000 times and does not damage, and it is stretched
Shear strength only loses 5.7%, shows excellent fatigue performance.
To sum up, comparative example 1-5 and comparative example 2, embodiment 1-5 is due to using the hyperbranched poly silicon oxygen with low viscosity
Alkane not only has high tenacity and high fatigue performance as toughener, but also has both excellent processing performance.
It is not for limiting claim, any this field skill although the present invention is disclosed as above with preferred embodiment
Art personnel without departing from the inventive concept of the premise, can make several possible variations and modification, therefore of the invention
Protection scope should be subject to the range that the claims in the present invention are defined.
Claims (9)
1. a kind of adhesive, mainly contains epoxy resin, which is characterized in that the adhesive also contains with epoxy-functional
Hyperbranched polyorganosiloxane, wherein the weight ratio of epoxy resin described in the adhesive and the hyperbranched polyorganosiloxane is
100:(5~30).
2. adhesive according to claim 1, which is characterized in that the epoxy resin is bisphenol A type epoxy resin or rouge
Ring race epoxy resin.
3. adhesive according to claim 1, which is characterized in that the hyperbranched polyorganosiloxane with epoxy-functional
For the hyperbranched polyorganosiloxane synthesized with KH-560.
4. adhesive according to claim 1, which is characterized in that the adhesive further contains toughener, wherein institute
The weight ratio for stating epoxy resin described in adhesive, the hyperbranched polyorganosiloxane and the toughener is 100:(5~30):
(5~50), the toughener are response type toughener, and preferably polysulfide rubber, carboxylated nitrile rubber or epoxy organosilicon is poly-
Close object.
5. adhesive according to claim 1, which is characterized in that the adhesive further contains filler, the gluing
The weight ratio of epoxy resin described in agent, the hyperbranched polyorganosiloxane and the filler is 100:(5~30): (1~100),
The filler is preferably fumed silica, talcum powder, clay or calcite.
6. adhesive according to claim 1, which is characterized in that the adhesive further contains amine curing agent,
Described in the weight ratio of epoxy resin, the hyperbranched polyorganosiloxane and the amine curing agent described in adhesive be 100:
(5~30): (2~50), the amine curing agent are aliphatic polyamine organic matter, and preferably hexamethylene diamine, more ethylene is more
Amine or curing agent by diketone acrylamide and diethylenetriamines addition.
7. adhesive according to claim 1, which is characterized in that the adhesive further contains curing accelerator,
Described in epoxy resin, the hyperbranched polyorganosiloxane and described 2,4,6- tri- (dimethylamino methyl) benzene described in adhesive
The weight ratio of phenol be 100:(5~30): (0.1~1), the curing accelerator be tertiary amine organic matter, preferably 2,4,6- tri- (two
Methyaminomethyl) phenol.
8. adhesive according to claim 1, which is characterized in that the adhesive enhances composite material for viscose fibre
And metal.
9. a kind of electrochemical appliance comprising fibre reinforced composites element and hardware, the fiber-reinforced composite material
Material element and the hardware are combined as a whole by adhesive described in any one of claim 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810149723.6A CN110157368A (en) | 2018-02-13 | 2018-02-13 | Adhesive and electrochemical device using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810149723.6A CN110157368A (en) | 2018-02-13 | 2018-02-13 | Adhesive and electrochemical device using same |
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| CN110157368A true CN110157368A (en) | 2019-08-23 |
Family
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| CN201810149723.6A Pending CN110157368A (en) | 2018-02-13 | 2018-02-13 | Adhesive and electrochemical device using same |
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2018
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| CN1454956A (en) * | 2003-05-19 | 2003-11-12 | 上海小糸车灯有限公司 | Single-component high-elasticity epoxy adhesive |
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| CN101724226A (en) * | 2009-11-20 | 2010-06-09 | 苏州大学 | Modified hot setting resin and preparation method thereof |
| CN101974227A (en) * | 2010-05-20 | 2011-02-16 | 复旦大学 | Low-stress epoxy/organic silicon/POSS nano hybrid material, and preparation method and application thereof |
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Application publication date: 20190823 |