CN107189701A - A kind of high temperature resistant anaerobism acrylic acid adhesive - Google Patents
A kind of high temperature resistant anaerobism acrylic acid adhesive Download PDFInfo
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- CN107189701A CN107189701A CN201710533689.8A CN201710533689A CN107189701A CN 107189701 A CN107189701 A CN 107189701A CN 201710533689 A CN201710533689 A CN 201710533689A CN 107189701 A CN107189701 A CN 107189701A
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- high temperature
- temperature resistant
- anaerobism
- acrylic acid
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- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- 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
- C09J11/06—Non-macromolecular additives organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a kind of high temperature resistant anaerobism acrylic acid adhesive, and by weight, the preparing raw material of the adhesive is included：100 parts of acrylated oligomer；1 13 parts of initiator；0.01 8 parts of accelerator；0.01 5 parts of kicker；0.1 6 parts of stabilizer.
Description
Technical field
The present invention relates to adhesive and adhesive product field, more particularly to a kind of high temperature resistant anaerobism acrylic acid adhesive.
Technical background
Extensively, preparation technology is simple for acrylate adhesive raw material sources, and rapid with drying and moulding, the transparency is good,
There is good bond performance to multiple material, and weatherability, water resistance, chemical proofing are also good.Particularly to hydrophobic table
Facestock material also has excellent cohesiveness, and the resistance to weathering of this rubber-like adhesive can be more excellent, and easy to use, bonding connects
Head durability is good.
Fire resistant anaerobic adhesive stick is met beyond certain temperature requirement, it is necessary to meet combination property：(1) have
Good ermal physics and thermo-chemical stability；(2) there is good processability；(3) in higher temperature and the condition of work used
Under, there are higher adhesion strength and preferable physical and mechanical properties and this performance can be effectively kept within the defined time.
Anaerobic adhesive also has following uniqueness：(1) viscosity of anaerobic adhesive can by macromolecule (methyl) acrylate with
Relative proportions regulation between (methyl) acrylate of low molecule amount, spread of viscosity is wide.When viscosity is adjusted, only need to add
The monomer of low molecule amount, therefore anaerobic adhesive cure shrinkage is less, is glued interface profit small；(2) anaerobic adhesive at room temperature can
Solidification, some gluded joints can even be used at relatively high temperatures, therefore can save the energy using anaerobic adhesive, be convenient for certainly
Dynamicization continuous productive process；(3) anaerobic adhesive is one pack system glue, and steady quality is easy to use, and other containers are not stain, and glue consumption is saved, nothing
Waste, glue-joint strength excursion is big, is easy to user to select；(4) permeability of anaerobic adhesive, absorbing, good airproof performance, typically
Solvent-free volatilization, it is nuisanceless when using to produce；(5) glue of the outside glue-line of anaerobic adhesive gluded joint and air contact does not solidify,
So understanding that these remaining glue are more convenient.
At present, the temperature requirement of anaerobism agent is general at 150 DEG C or so, and conventional method is to seek heat-resisting monomer or add
Enter heat resistance preferable organic or inorganic thing in itself, this kind of method often possesses valency to the compatibility between the raw material of adhesive
High requirement, therefore the storage cycle of product is shorter, longer-term storage can decompose；Also or produce adhesive strength decline, scratch
The more low phenomenon of song.
For above-mentioned situation, the present invention provides a kind of high temperature resistant anaerobism acrylic acid adhesive, is possessing high temperature resistant, anaerobism
Under performance, possesses adhesion strength height, flexural property is good, can solidify at room temperature, do not decompose the excellent performances such as generation pollutant.
The content of the invention
The present invention provides a kind of high temperature resistant anaerobism acrylic acid adhesive, by weight, the preparing raw material of the adhesive
Comprising：
As one embodiment of the present invention, by weight, the preparing raw material of the adhesive is included：
As one embodiment of the present invention, by weight, the preparing raw material of the adhesive is also included：
0.01-10 parts of polymerization inhibitor；
0.01-8 parts of thixotropic agent.
As one embodiment of the present invention, by weight, the preparing raw material of the adhesive is also included：
3 parts of polymerization inhibitor；
3 parts of thixotropic agent.
As one embodiment of the present invention, the acrylated oligomer is acrylic ester prepolymer and epoxy acrylic
Ester prepolymer.
As one embodiment of the present invention, the initiator is that peroxide initiator or redox system trigger
Agent.
As one embodiment of the present invention, the accelerator is N, N- dimethyl-p-toluidines or triethylamine.
As one embodiment of the present invention, the kicker is benzoic sulfimide or phthalimide.
As one embodiment of the present invention, the stabilizer is 8-hydroxyquinoline or ethylenediamine tetra-acetic acid.
It is a kind of to be the step of prepare a kind of preparation method of high temperature resistant anaerobism acrylic acid adhesive, the preparation method：
Stabilizer is added in acrylated oligomer by S01 by weight, and stirring is to being completely dissolved；
S02 adds accelerator and kicker into step S01, and stirring is to being completely dissolved；
S03 adds the surplus stock in addition to initiator, stirring to substantially uniformity into step S02；
S04 adds initiator into step S03, after stirring, and obtains high temperature resistant anaerobism acrylic acid adhesive.
Embodiment
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, it is not included the material in addition to materials of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item or event that describe thereafter may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this specific
Quantity, includes the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.In some examples, approximately
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope is limited can be with
Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, the indefinite article " one kind " and " one " before key element of the present invention or component are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means by the polymerizable compound prepared by the monomer that polymerize identical or different type.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " EVA ".
" EVA " means by polymerizeing polymer prepared by least two different monomers.Generic term " EVA " includes
(its is general with term " terpolymer " for term " copolymer " (it is typically to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It also includes the polymerization planted monomer by polymerization four or more and manufactured
Thing." blend " means two or more polymer by polymerizeing formed by physics or chemistry method jointly mixing
Thing.
The present invention provides a kind of high temperature resistant anaerobism acrylic acid adhesive, by weight, the preparing raw material of the adhesive
Comprising：
The preparing raw material of the adhesive is also included：
0.01-10 parts of polymerization inhibitor；
0.01-8 parts of thixotropic agent.
Acrylated oligomer
Acrylated oligomer, is a class active prepolymer, it is possible to provide most of performance of adhesive, the most frequently used oligomer
There are four major classes：Epoxy acrylate, urethane acrylate, polyester acrylate and acrylate.
In the present invention, the acrylated oligomer is acrylic ester prepolymer and epoxy acrylic ester prepolymer (parts by weight
Than for 5：1).
The epoxy acrylic ester prepolymer is that hyperbranched epoxy resin is prepared with (methyl) propylene acid reaction.
In the present invention, the preparation method of the epoxy acrylic ester prepolymer is as follows：
1) preparation of hyperbranched epoxy resin：Using hyperbranched hydroxyl polyester and hexahydrophthalic anhydride according to hydroxyl and
The mol ratio 1 of acid anhydrides：The ratio of (4-40), at a temperature of 100-160 DEG C, reacts, hyperbranched hydroxyl under inert gas shielding
The hydroxyl of polymer carries out anhydride esterifying, forms the hyperbranched hydroxyl polyester of the carboxylated containing carboxyl functional group；
2) by step 1) synthesis the hyperbranched hydroxy polymer of carboxylated and epoxy resin according to carboxyl functional group and epoxy
The mol ratio of functional group about 1:2 ratio, is reacted at a temperature of 100-160 DEG C, is reacted, is surpassed under inert gas shielding
Branch epoxy resins.(weight average molecular weight of the hyperbranched epoxy resin is between 2000-30000.)
3) hyperbranched epoxy resin and hydroquinones of ormal weight are added in reaction bulb and stir and heat, treat temperature liter
Up to 100 DEG C~110 DEG C or so start that acrylic acid and DMA is added dropwise, and control time for adding is added dropwise in 1h or so
Finish and start to survey acid number after half an hour, start cooling after acid number is constant, added when temperature is down to 90 DEG C or so dissolved with regulation
The styrene solution latting drown of hydroquinones is measured, 40 DEG C are cooled to after mixing half an hour and stops stirring, discharging, is transferred in container
Sealing preserve is stand-by.
In the present invention, the preparation method of the acrylic ester prepolymer is as follows：By dissolved with the methyl-prop of benzoyl peroxide
E pioic acid methyl ester, which is added in reaction bulb, to be stirred and heats, and voltage controlling reaction temperature is adjusted, when temperature rises to 85 DEG C or so
The viscosity of reactant is measured after stable reaction half an hour using grignard pipe, reaches and ormal weight is added after defined viscosity dissolved with to benzene
The methyl methacrylate of diphenol, is cooled to 40 DEG C and stops stirring, discharging after mixing a period of time, be transferred to seal in container and protect
Deposit stand-by.
In the present invention, model HyPer of the hyperbranched hydroxyl polyester purchase from Wuhan hyperbranched resin Co., Ltd
H40 series H402 products.
Initiator：Heretofore described initiator is peroxide initiator or redox system initiator, such as mistake
Aoxidize dibenzoyl, potassium peroxydisulfate or hydrogen peroxide-ferrous salt.
Heretofore described initiator is dibenzoyl peroxide.
Accelerator：Heretofore described accelerator is N, accelerine or triethylamine.
As a kind of preferred embodiment of the present invention, the accelerator is DMA.
Kicker：Heretofore described kicker is benzoic sulfimide or phthalimide.
As one embodiment of the present invention, the kicker is benzoic sulfimide.
Stabilizer：Heretofore described stabilizer is 8-hydroxyquinoline or ethylenediamine tetra-acetic acid.
8-hydroxyquinoline is selected from as stabilizer described in one embodiment of the present invention.
Polymerization inhibitor：Heretofore described polymerization inhibitor is that 1,4- naphthoquinones and 1,2- naphthoquinones are 1 according to weight ratio：1 is mixed to get.
Thixotropic agent：Heretofore described thixotropic agent is polyamide wax.
As one embodiment of the present invention, by weight, the preparing raw material of the adhesive is included：
The preparing raw material of the adhesive is also included：
3 parts of polymerization inhibitor；
3 parts of thixotropic agent.
As one embodiment of the present invention, the preparing raw material of the high temperature resistant anaerobism acrylic acid adhesive is also included
Bicyclic [2.2.2] octane (2,3,5,6,7,8-hexamethylenebicyc of 2,3,5,6,7,8- hexa-methylenes of 0.5 parts by weight
Lo [2.2.2] octane), No. CAS is 74772-12-6, is bought from Shenzhen Ai Tuo Chemical Co., Ltd.s.
As one embodiment of the present invention, the preparing raw material of the high temperature resistant anaerobism acrylic acid adhesive also includes 1
The hyperbranched chitosan of parts by weight.
In the present invention, the preparation method of the hyperbranched chitosan is as follows：50g chitosans are dissolved in 1000mL5%'s
Aqueous acetic acid is simultaneously cooled to 4 DEG C.By 5g NaNO2It is dissolved in after 50mL water and is added dropwise to above-mentioned chitosan solution, 9 is reacted at 0 DEG C
Hour, add the dense NaOH aqueous solution and all separated out to precipitation, filtering, and with methanol and water washing repeatedly, it is dried in vacuo what is obtained
Low-molecular weight chitoglycan with aldehyde radical end group.Low-molecular weight chitoglycan be classified through methanol extraction after product (Mw=2300,
Mw/Mn=1.5, GPC/ light scattering method) be dissolved in stirred 1 hour at 0.1M acetic acid (2mg/mL), 10 DEG C after 0.1M NaOH are added dropwise
The aqueous solution to pH be 5.5.Continuation adds NaCNBH of 1.0 times equivalent to aldehyde radical molal quantity after stirring 2 hours3, react at 10 DEG C
Same amount of NaCNBH is added after 24 hours3, continue to react 72 hours.Period control ph is not higher than 6.5.Reaction solution sand
Core funnel is filtered, and filtrate is repeatedly washed with methanol, water with 3 times of methanol extractions.It is dried in vacuo at 40 DEG C of product after washing,
Obtain hyperbranched chitosan standby；100 grams of hyperbranched chitosans are taken, the ferrous sulfate for being added to 350 milliliter of 5 mol/L is water-soluble
In liquid (contain 1.75 moles, about 266 grams of ferrous sulfate), it is stirred vigorously after 60 minutes, filters, 1500 milliliters of deionized water of filter cake
Cyclic washing 6 times, obtains being chelated with the hyperbranched chitosan of ferrous element.
As one embodiment of the present invention, the preparing raw material of the high temperature resistant anaerobism acrylic acid adhesive also includes 1
The 4,8- dihydroxy quinaldic acids of parts by weight.
The second aspect of the present invention provides a kind of preparation side for preparing a kind of above-mentioned high temperature resistant anaerobism acrylic acid adhesive
Method, it is characterised in that be the step of the preparation method：
Stabilizer is added in acrylated oligomer by S01 by weight, and stirring is to being completely dissolved；
S02 adds accelerator and kicker into step S01, and stirring is to being completely dissolved；
S03 adds the surplus stock in addition to initiator, stirring to substantially uniformity into step S02；
S04 adds initiator into step S03, after stirring, and obtains high temperature resistant anaerobism acrylic acid adhesive.
Mechanism is explained：High temperature resistant anaerobism acrylic acid adhesive that the present invention is prepared, not only can be in anoxic, room temperature
Solidify under environment, outstanding glueability can also be kept at high temperature；Product memory cycle time is long simultaneously, maintains adhesivity
The time of energy is also very long, is not in adhesive strength decline, the more low phenomenon of flexibility in one section of long time；Its is possible
Reason is because the preparing raw material of adhesive is comprising bicyclic [2.2.2] octane of 2,3,5,6,7,8- hexa-methylenes in the present invention, surpass
Branched chitosan and 4,8- dihydroxy quinaldic acid.Because being chelated with ferrous ion, the Asia in the hyperbranched chitosan
Iron ion can promote the performance of the high temperature resistant anaerobism of adhesive, but can produce ferric ion, three after ferrous ion reaction
The long term accumulation presence of valency iron ion can influence the performance of adhesive；Heretofore described 2,3,5,6,7,8- hexa-methylenes are bicyclic
The addition of [2.2.2] octane and hyperbranched chitosan can then to form benign follow between ferrous ion and ferric ion
Ring, it is to avoid harmful effect occur.
Embodiment 1：Present embodiment provides a kind of high temperature resistant anaerobism acrylic acid adhesive, by weight, the glue
The preparing raw material of stick is included：
Embodiment 2：A kind of high temperature resistant anaerobism acrylic acid adhesive described in embodiment 1, by weight, the glue
The preparing raw material of stick is included：
Embodiment 3：A kind of high temperature resistant anaerobism acrylic acid adhesive described in embodiment 1, by weight, the glue
The preparing raw material of stick is also included：
0.01-10 parts of polymerization inhibitor；
0.01-8 parts of thixotropic agent.
Embodiment 4：A kind of high temperature resistant anaerobism acrylic acid adhesive described in embodiment 1, by weight, the glue
The preparing raw material of stick is also included：
3 parts of polymerization inhibitor；
3 parts of thixotropic agent.
Embodiment 5：A kind of high temperature resistant anaerobism acrylic acid adhesive described in embodiment 1, the acrylated oligomer
For acrylic ester prepolymer and epoxy acrylic ester prepolymer.
Embodiment 6：A kind of high temperature resistant anaerobism acrylic acid adhesive described in embodiment 1, the initiator is peroxide
Compound initiator or redox system initiator.
Embodiment 7：A kind of high temperature resistant anaerobism acrylic acid adhesive described in embodiment 1, the accelerator is N, N-
Dimethylaniline or triethylamine.
Embodiment 8：A kind of high temperature resistant anaerobism acrylic acid adhesive described in embodiment 1, the kicker is neighbour
Sulphonyl benzoylimino or phthalimide.
Embodiment 9：A kind of high temperature resistant anaerobism acrylic acid adhesive described in embodiment 1, the stabilizer is 8- hydroxyls
Base quinoline or ethylenediamine tetra-acetic acid.
Embodiment 10：A kind of a kind of high temperature resistant anaerobism acrylic acid adhesive prepared described in embodiment any one of 1-9
Preparation method, be the step of the preparation method：
Stabilizer is added in acrylated oligomer by S01 by weight, and stirring is to being completely dissolved；
S02 adds accelerator and kicker into step S01, and stirring is to being completely dissolved；
S03 adds the surplus stock in addition to initiator, stirring to substantially uniformity into step S02；
S04 adds initiator into step S03, after stirring, and obtains high temperature resistant anaerobism acrylic acid adhesive.
The present invention is specifically described below by embodiment.It is necessarily pointed out that, following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, raw materials used is all commercially available.
Embodiment 1：The present embodiment provides a kind of high temperature resistant anaerobism acrylic acid adhesive, by weight, the adhesive
Preparing raw material include：
The acrylated oligomer is the epoxy acrylate pre-polymerization of 83 parts by weight propylene acid esters prepolymers and 17 parts by weight
Thing.
The preparation method of the epoxy acrylic ester prepolymer is as follows：
1) preparation of hyperbranched epoxy resin：Using hyperbranched hydroxyl polyester and hexahydrophthalic anhydride according to hydroxyl and
The mol ratio 1 of acid anhydrides：12 ratio, at a temperature of 150 DEG C, reacts under inert gas shielding, hyperbranched hydroxy polymer
Hydroxyl carries out anhydride esterifying, forms the hyperbranched hydroxyl polyester of the carboxylated containing carboxyl functional group；
2) by step 1) synthesis the hyperbranched hydroxy polymer of carboxylated and epoxy resin according to carboxyl functional group and epoxy
The mol ratio of functional group about 1:2 ratio, is reacted at a temperature of 150 DEG C, is reacted under inert gas shielding, is obtained hyperbranched
Epoxy resin.
3) hyperbranched epoxy resin and hydroquinones of ormal weight are added in reaction bulb and stir and heat, treat temperature liter
Up to 100 DEG C~110 DEG C or so start that acrylic acid and DMA is added dropwise, and control time for adding is added dropwise in 1h or so
Finish and start to survey acid number after half an hour, start cooling after acid number is constant, added when temperature is down to 90 DEG C or so dissolved with regulation
The styrene solution latting drown of hydroquinones is measured, 40 DEG C are cooled to after mixing half an hour and stops stirring, discharging, is transferred in container
Sealing preserve is stand-by.
The preparation method of the acrylic ester prepolymer is as follows：Methyl methacrylate dissolved with benzoyl peroxide is added
Enter and stir and heat into reaction bulb, adjust voltage controlling reaction temperature, the stable reaction half when temperature rises to 85 DEG C or so
The viscosity of reactant is measured after hour using grignard pipe, reaches and methyl of the ormal weight dissolved with hydroquinones is added after defined viscosity
Methyl acrylate, is cooled to 40 DEG C and stops stirring, discharging, be transferred to sealing preserve in container stand-by after mixing a period of time.
In the present embodiment, model of the hyperbranched hydroxyl polyester purchase from Wuhan hyperbranched resin Co., Ltd
HyPer H40 series H402 products.
The initiator is dibenzoyl peroxide.
The accelerator is N, accelerine.
The kicker is benzoic sulfimide.
The stabilizer is selected from 8-hydroxyquinoline.
The polymerization inhibitor is that 1,4- naphthoquinones and 1,2- naphthoquinones are 1 according to weight ratio：1 is mixed to get.
The thixotropic agent is polyamide wax.
The preparation method of the hyperbranched chitosan is as follows：50g chitosans are dissolved in 1000mL5% aqueous acetic acid
And it is cooled to 4 DEG C.By 5g NaNO2It is dissolved in after 50mL water and is added dropwise to above-mentioned chitosan solution, reacted 9 hours at 0 DEG C, is added
The dense NaOH aqueous solution is all separated out to precipitation, filtering, and with methanol and water washing repeatedly, what vacuum drying was obtained carries aldehyde radical end
The low-molecular weight chitoglycan of base.Low-molecular weight chitoglycan be classified through methanol extraction after product (Mw=2300, Mw/Mn=1.5,
GPC/ light scattering methods) be dissolved in stirred 1 hour at 0.1M acetic acid (2mg/mL), 10 DEG C after the 0.1M NaOH aqueous solution is added dropwise to pH
For 5.5.Continuation adds NaCNBH of 1.0 times equivalent to aldehyde radical molal quantity after stirring 2 hours3, at 10 DEG C after reaction 24 hours again
Add same amount of NaCNBH3, continue to react 72 hours.Period control ph is not higher than 6.5.Reaction solution sand core funnel mistake
Filter, filtrate is repeatedly washed with methanol, water with 3 times of methanol extractions.It is dried in vacuo, is overspend at 40 DEG C of product after washing
Change chitosan standby；Take in 100 grams of hyperbranched chitosans, the ferrous sulfate aqueous solution for being added to 350 milliliter of 5 mol/L and (contain
1.75 moles, about 266 grams of ferrous sulfate), it is stirred vigorously after 60 minutes, filters, filter cake is washed for 1500 milliliters repeatedly with deionized water
Wash 6 times, obtain being chelated with the hyperbranched chitosan of ferrous element.
Bicyclic [2.2.2] octane of 2,3,5,6,7,8- hexa-methylenes is bought from Shenzhen Ai Tuo Chemical Co., Ltd.s.
The second aspect of the present embodiment provides a kind of preparation for preparing a kind of above-mentioned high temperature resistant anaerobism acrylic acid adhesive
Method, it is characterised in that be the step of the preparation method：
Stabilizer is added in acrylated oligomer by S01 by weight, and stirring is to being completely dissolved；
S02 adds accelerator and kicker into step S01, and stirring is to being completely dissolved；
S03 adds the surplus stock in addition to initiator, stirring to substantially uniformity into step S02；
S04 adds initiator into step S03, after stirring, and obtains high temperature resistant anaerobism acrylic acid adhesive.
Embodiment 2：Difference with embodiment 1 is that the preparing raw material of the adhesive is included：
Embodiment 3：Difference with embodiment 1 is that the preparing raw material of the adhesive is included：
Embodiment 4：Difference with embodiment 1 is that it is bicyclic that preparing raw material does not include 2,3,5,6,7,8- hexa-methylenes
[2.2.2] octane.
Embodiment 5：Difference with embodiment 1 is that preparing raw material does not include hyperbranched chitosan.
Embodiment 6：Difference with embodiment 1 is that preparing raw material does not include 4,8- dihydroxy quinaldic acids.
Embodiment 7：Difference with embodiment 1 is that preparing raw material does not include epoxy acrylic ester prepolymer.
Embodiment 8：Difference with embodiment 1 is that the polymerization inhibitor is 1,4-naphthoquinone.
Embodiment 9：Difference with embodiment 1 is that the preparation method of the hyperbranched chitosan is as follows：50g shells are gathered
Sugar is dissolved in 1000mL5% aqueous acetic acid and is cooled to 4 DEG C.By 5g NaNO2It is dissolved in after 50mL water and is added dropwise to above-mentioned shell
Glycan solution, reacts 9 hours at 0 DEG C, adds the dense NaOH aqueous solution and all separates out to precipitating, filtering, and with methanol and water washing
Repeatedly, it is dried in vacuo the obtained low-molecular weight chitoglycan with aldehyde radical end group.Low-molecular weight chitoglycan is classified through methanol extraction
Product (Mw=2300, Mw/Mn=1.5, GPC/ light scattering method) afterwards, which is dissolved at 0.1M acetic acid (2mg/mL), 10 DEG C, stirs 1
Hour after be added dropwise the 0.1M NaOH aqueous solution to pH be 5.5.Continue to add after stirring 2 hours equivalent to 1.0 times of aldehyde radical molal quantity
NaCNBH3, reaction adds same amount of NaCNBH after 24 hours at 10 DEG C3, continue to react 72 hours.Period control ph is not
Higher than 6.5.Reaction solution is filtered with sand core funnel, and filtrate is repeatedly washed with methanol, water with 3 times of methanol extractions.Production after washing
It is dried in vacuo at 40 DEG C of thing, obtains hyperbranched chitosan.
Embodiment 10：Difference with embodiment 1 is that it is bicyclic that preparing raw material does not include 2,3,5,6,7,8- hexa-methylenes
[2.2.2] octane and hyperbranched chitosan.
Test：
Embodiment 1：Material is weighed according to formula embodiment 1 Suo Shi, 5~10min is stirred at room temperature, is stirred for
It is even, obtain room curing and high temperature resistant anaerobic adhesive.The a certain amount of room curing and high temperature resistant anaerobic adhesive is taken to be used to be bonded stone
Black test piece, room temperature, which is placed 7 days, to be solidified.Room temperature shear strength is 10.3MPa；Under the conditions of 1000 DEG C, 5min on-line testings are incubated
Adhesive strength is 5.0MPa.The sample after solidification is subjected to the processing of immersion in 24 hours again, room temperature shear strength is 10.1MPa；
Under the conditions of 1000 DEG C, insulation 5min on-line testings adhesive strength is 4.5MPa.
Embodiment 2：Material is weighed according to formula embodiment 2 Suo Shi, 5~10min is stirred at room temperature, is stirred for
It is even, obtain room curing and high temperature resistant anaerobic adhesive.The a certain amount of room curing and high temperature resistant anaerobic adhesive is taken to be used to be bonded stone
Black test piece, room temperature, which is placed 7 days, to be solidified.Room temperature shear strength is 9.9MPa；Under the conditions of 1000 DEG C, insulation 5min on-line testings are glued
Intensity is connect for 4.2MPa.The sample after solidification is subjected to the processing of immersion in 24 hours again, room temperature shear strength is 9.8MPa；1000
Under the conditions of DEG C, insulation 5min on-line testings adhesive strength is 4.0MPa.
Embodiment 3：Material is weighed according to formula embodiment 3 Suo Shi, 5~10min is stirred at room temperature, is stirred for
It is even, obtain room curing and high temperature resistant anaerobic adhesive.The a certain amount of room curing and high temperature resistant anaerobic adhesive is taken to be used to be bonded stone
Black test piece, room temperature, which is placed 7 days, to be solidified.Room temperature shear strength is 7.5MPa；Under the conditions of 1000 DEG C, insulation 5min on-line testings are glued
Intensity is connect for 2.0MPa.The sample after solidification is subjected to the processing of immersion in 24 hours again, room temperature shear strength is 6.5MPa；1000
Under the conditions of DEG C, insulation 5min on-line testings adhesive strength is 1.3MPa.
Embodiment 4：Material is weighed according to formula embodiment 4 Suo Shi, 5~10min is stirred at room temperature, is stirred for
It is even, obtain room curing and high temperature resistant anaerobic adhesive.The a certain amount of room curing and high temperature resistant anaerobic adhesive is taken to be used to be bonded stone
Black test piece, room temperature, which is placed 7 days, to be solidified.Room temperature shear strength is 4.5MPa；Under the conditions of 1000 DEG C, insulation 5min on-line testings are glued
Intensity is connect for 1.2MPa.The sample after solidification is subjected to the processing of immersion in 24 hours again, room temperature shear strength is 4.0MPa；1000
Under the conditions of DEG C, insulation 5min on-line testings adhesive strength is 1.0MPa.
Embodiment 5：Material is weighed according to formula embodiment 5 Suo Shi, 5~10min is stirred at room temperature, is stirred for
It is even, obtain room curing and high temperature resistant anaerobic adhesive.The a certain amount of room curing and high temperature resistant anaerobic adhesive is taken to be used to be bonded stone
Black test piece, room temperature, which is placed 7 days, to be solidified.Room temperature shear strength is 4.3MPa；Under the conditions of 1000 DEG C, insulation 5min on-line testings are glued
Intensity is connect for 1.1MPa.The sample after solidification is subjected to the processing of immersion in 24 hours again, room temperature shear strength is 4.1MPa；1000
Under the conditions of DEG C, insulation 5min on-line testings adhesive strength is 1.0MPa.
Embodiment 6：Material is weighed according to formula embodiment 6 Suo Shi, 5~10min is stirred at room temperature, is stirred for
It is even, obtain room curing and high temperature resistant anaerobic adhesive.The a certain amount of room curing and high temperature resistant anaerobic adhesive is taken to be used to be bonded stone
Black test piece, room temperature, which is placed 7 days, to be solidified.Room temperature shear strength is 4.4MPa；Under the conditions of 1000 DEG C, insulation 5min on-line testings are glued
Intensity is connect for 1.2MPa.The sample after solidification is subjected to the processing of immersion in 24 hours again, room temperature shear strength is 4.0MPa；1000
Under the conditions of DEG C, insulation 5min on-line testings adhesive strength is 0.9MPa.
Embodiment 7：Material is weighed according to formula embodiment 7 Suo Shi, 5~10min is stirred at room temperature, is stirred for
It is even, obtain room curing and high temperature resistant anaerobic adhesive.The a certain amount of room curing and high temperature resistant anaerobic adhesive is taken to be used to be bonded stone
Black test piece, room temperature, which is placed 7 days, to be solidified.Room temperature shear strength is 2.3MPa；Under the conditions of 1000 DEG C, insulation 5min on-line testings are glued
Intensity is connect for 0.5MPa.The sample after solidification is subjected to the processing of immersion in 24 hours again, room temperature shear strength is 2.2MPa；1000
Under the conditions of DEG C, insulation 5min on-line testings adhesive strength is 0.4MPa.
Embodiment 8：Material is weighed according to formula embodiment 8 Suo Shi, 5~10min is stirred at room temperature, is stirred for
It is even, obtain room curing and high temperature resistant anaerobic adhesive.The a certain amount of room curing and high temperature resistant anaerobic adhesive is taken to be used to be bonded stone
Black test piece, room temperature, which is placed 7 days, to be solidified.Room temperature shear strength is 8.0MPa；Under the conditions of 1000 DEG C, insulation 5min on-line testings are glued
Intensity is connect for 2.1MPa.The sample after solidification is subjected to the processing of immersion in 24 hours again, room temperature shear strength is 7.5MPa；1000
Under the conditions of DEG C, insulation 5min on-line testings adhesive strength is 2.0MPa.
Embodiment 9：Material is weighed according to formula embodiment 9 Suo Shi, 5~10min is stirred at room temperature, is stirred for
It is even, obtain room curing and high temperature resistant anaerobic adhesive.The a certain amount of room curing and high temperature resistant anaerobic adhesive is taken to be used to be bonded stone
Black test piece, room temperature, which is placed 7 days, to be solidified.Room temperature shear strength is 5.9MPa；Under the conditions of 1000 DEG C, insulation 5min on-line testings are glued
Intensity is connect for 1.8MPa.The sample after solidification is subjected to the processing of immersion in 24 hours again, room temperature shear strength is 5.5MPa；1000
Under the conditions of DEG C, insulation 5min on-line testings adhesive strength is 1.6MPa.
Embodiment 10：Material is weighed according to formula embodiment 10 Suo Shi, 5~10min is stirred at room temperature, is stirred for
It is even, obtain room curing and high temperature resistant anaerobic adhesive.The a certain amount of room curing and high temperature resistant anaerobic adhesive is taken to be used to be bonded stone
Black test piece, room temperature, which is placed 7 days, to be solidified.Room temperature shear strength is 2.4MPa；Under the conditions of 1000 DEG C, insulation 5min on-line testings are glued
Intensity is connect for 0.5MPa.The sample after solidification is subjected to the processing of immersion in 24 hours again, room temperature shear strength is 2.3MPa；1000
Under the conditions of DEG C, insulation 5min on-line testings adhesive strength is 0.4MPa.
Foregoing example is merely illustrative, some features of the feature for explaining the present invention.Appended claim
The scope as wide as possible for requiring to be contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction.And the progress in science and technology by formed language performance it is inaccurate due to and not
The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case
Claim is covered.
Claims (10)
1. a kind of high temperature resistant anaerobism acrylic acid adhesive, it is characterised in that by weight, the preparing raw material bag of the adhesive
Contain：
2. a kind of high temperature resistant anaerobism acrylic acid adhesive described in claim 1, it is characterised in that by weight, the glue
The preparing raw material of stick is included：
3. a kind of high temperature resistant anaerobism acrylic acid adhesive described in claim 1, it is characterised in that by weight, the glue
The preparing raw material of stick is also included：
0.01-10 parts of polymerization inhibitor；
0.01-8 parts of thixotropic agent.
4. a kind of high temperature resistant anaerobism acrylic acid adhesive described in claim 1, it is characterised in that by weight, the glue
The preparing raw material of stick is also included：
3 parts of polymerization inhibitor；
3 parts of thixotropic agent.
5. a kind of high temperature resistant anaerobism acrylic acid adhesive described in claim 1, it is characterised in that the acrylated oligomer is
Acrylic ester prepolymer and epoxy acrylic ester prepolymer.
6. a kind of high temperature resistant anaerobism acrylic acid adhesive described in claim 1, it is characterised in that the initiator is peroxidating
Thing initiator or redox system initiator.
7. a kind of high temperature resistant anaerobism acrylic acid adhesive described in claim 1, it is characterised in that the accelerator is N, N- bis-
Methylaniline or triethylamine.
8. a kind of high temperature resistant anaerobism acrylic acid adhesive described in claim 1, it is characterised in that the kicker is adjacent sulphur
Acyl benzoylimino or phthalimide.
9. a kind of high temperature resistant anaerobism acrylic acid adhesive described in claim 1, it is characterised in that the stabilizer is 8- hydroxyls
Quinoline or ethylenediamine tetra-acetic acid.
10. a kind of a kind of preparation method of the high temperature resistant anaerobism acrylic acid adhesive prepared described in claim any one of 1-9, its
It is characterised by, is the step of the preparation method：
Stabilizer is added in acrylated oligomer by S01 by weight, and stirring is to being completely dissolved；
S02 adds accelerator and kicker into step S01, and stirring is to being completely dissolved；
S03 adds the surplus stock in addition to initiator, stirring to substantially uniformity into step S02；
S04 adds initiator into step S03, after stirring, and obtains high temperature resistant anaerobism acrylic acid adhesive.
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| CN201710533689.8A CN107189701A (en) | 2017-07-03 | 2017-07-03 | A kind of high temperature resistant anaerobism acrylic acid adhesive |
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| CN201710533689.8A CN107189701A (en) | 2017-07-03 | 2017-07-03 | A kind of high temperature resistant anaerobism acrylic acid adhesive |
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| CN201710533689.8A Pending CN107189701A (en) | 2017-07-03 | 2017-07-03 | A kind of high temperature resistant anaerobism acrylic acid adhesive |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110643317A (en) * | 2019-09-25 | 2020-01-03 | 玉环鑫淼建材有限公司 | Anaerobic adhesive composition and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159471A (en) * | 1996-11-15 | 1997-09-17 | 北京市天山新材料技术公司 | Anaerobic glue and preparation method |
| CN101328395A (en) * | 2008-07-31 | 2008-12-24 | 广东恒大新材料科技有限公司 | Anaerobic oxygen rubber composition |
| CN101735734A (en) * | 2008-11-04 | 2010-06-16 | 广东恒大新材料科技有限公司 | Anaerobic adhesive initiator composite and anaerobic adhesive containing initiator |
| CN103160211A (en) * | 2011-12-19 | 2013-06-19 | 烟台德邦科技有限公司 | Solar crystalline silicon rod splicing glue and preparation method thereof |
| CN104762052A (en) * | 2015-04-10 | 2015-07-08 | 大连理工大学 | Organic one-component inserted bar glue and preparation method thereof |
-
2017
- 2017-07-03 CN CN201710533689.8A patent/CN107189701A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159471A (en) * | 1996-11-15 | 1997-09-17 | 北京市天山新材料技术公司 | Anaerobic glue and preparation method |
| CN101328395A (en) * | 2008-07-31 | 2008-12-24 | 广东恒大新材料科技有限公司 | Anaerobic oxygen rubber composition |
| CN101735734A (en) * | 2008-11-04 | 2010-06-16 | 广东恒大新材料科技有限公司 | Anaerobic adhesive initiator composite and anaerobic adhesive containing initiator |
| CN103160211A (en) * | 2011-12-19 | 2013-06-19 | 烟台德邦科技有限公司 | Solar crystalline silicon rod splicing glue and preparation method thereof |
| CN104762052A (en) * | 2015-04-10 | 2015-07-08 | 大连理工大学 | Organic one-component inserted bar glue and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110643317A (en) * | 2019-09-25 | 2020-01-03 | 玉环鑫淼建材有限公司 | Anaerobic adhesive composition and preparation method thereof |
| CN110643317B (en) * | 2019-09-25 | 2023-03-24 | 玉环鑫淼建材有限公司 | Anaerobic adhesive composition and preparation method thereof |
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Address after: 201199 Minhang District Xiangyang Road, Minhang District, Shanghai, No. 1358, 2 and 2 layers Applicant after: Shanghai Yu Xin Mstar Technology Ltd Address before: 201199 Minhang District Xiangyang Road, Minhang District, Shanghai, No. 1358, 2 and 2 layers Applicant before: Shanghai Dou Wei photovoltaic Science and Technology Ltd. |
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