CN108753229A - A kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat adhesive - Google Patents
A kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat adhesive Download PDFInfo
- Publication number
- CN108753229A CN108753229A CN201810641072.2A CN201810641072A CN108753229A CN 108753229 A CN108753229 A CN 108753229A CN 201810641072 A CN201810641072 A CN 201810641072A CN 108753229 A CN108753229 A CN 108753229A
- Authority
- CN
- China
- Prior art keywords
- parts
- temperature
- epoxy resin
- added
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of near-zero thermal expansion high-performance room-temperatures to cure inflatable boat adhesive, and the adhesive is made of following component：Epoxy resin, high-temperature-resistant epoxy resin, liquid nbr carboxyl terminal, modified polysulfide rubber, Expanding Monomer, modified bismaleimide, 4,4- diaminodiphenylmethane, phenolic resin micro mist, mica powder, flake asbestos, polyetheramine, amine terminated polyether, m-phenylene diamine (MPD), modifying epoxy resin by organosilicon.Adhesive made from treatment process of the present invention has near-zero thermal expansion, low temperature resistant, wear-resisting scratch resistance, heat safe feature.
Description
Technical field
The invention belongs to adhesive manufacturing fields, and in particular to a kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat glue
Glutinous agent.
Background technology
Though common epoxy resin adhesive has higher stretching and shear strength, peel strength is low, impact flexibility
Difference, heat resistance is low, and using being restricted, epoxy resin adhesive tends to occur volume contraction during solidification and use, and
It cracks, embedding or sealing structure is caused to be failed, especially in inflating based article, because of the cure shrinkage of epoxy resin,
So that the adhesive dosage that aerated materials bonding uses is increased and improve cost, and often can be because of the intrinsic of epoxy resin adhesive
Defect leads to seam crossing gas leakage, and water inlet influences to use, it is also possible to cause security risk.
Invention content
The purpose of the present invention is for existing problem, provide a kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat use
Adhesive.
A kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat adhesive, is made of following component：Liquid end carboxyl fourth
15 ~ 20 parts of nitrile rubber, 90 ~ 100 parts of epoxy resin, 90 ~ 100 parts of high-temperature-resistant epoxy resin, modifying epoxy resin by organosilicon 20 ~ 30
Part, 8 ~ 12 parts of polyetheramine：8 ~ 12 parts of m-phenylene diamine (MPD), 20 ~ 25 parts of 4,4- diaminodiphenylmethane, 5 ~ 7 parts of amine terminated polyether, mica
6 ~ 9 parts of powder, 13 ~ 17 parts of flake asbestos, 60 ~ 80 parts of phenolic resin micro mist.
A kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat adhesive, preparation method includes the following steps：（1）Group
Divide the preparation of A：Each substance first is weighed with parts by weight by above-mentioned formula, by liquid nbr carboxyl terminal, epoxy resin, resistance to height
Temperature epoxy resin, is mixed into blender modifying epoxy resin by organosilicon, and modifying epoxy resin by organosilicon is first then put into three
It in mouth bottle, is warming up to 110 DEG C and keeps the temperature 1h, remove the solvent in modifying epoxy resin by organosilicon, then other each substances are added to
It in there-necked flask, stirs evenly, the liquid for making stable is component A；
（2）The preparation of component B：10 parts of polyetheramine, 10 parts of m-phenylene diamine (MPD), 23 parts of 4,4- diaminodiphenylmethane, amine terminated polyether 6
Part, each substance is sufficiently mixed and stirs evenly to get component B at a temperature of 50 ~ 60 DEG C；
（3）The preparation of component C：By mica powder, flake asbestos, phenolic resin micro mist through crushing, sieves, after compounding, it is single that expansion is added
50 parts of body is sufficiently mixed uniformly.With the working life after glue, the proportioning of adhesive is generally between 4 ~ 5h：First component：Second
Component：Third component=5：1：4,25 ~ 35 DEG C of solidification temperature.
Further, the Expanding Monomer be two phenoxy group dichloromethane and 3,9- diethyl -3,9- dihydroxymethyls -1,5,
7,11- tetra- oxygen spiral shell [5,5] undecanoic mixtures；3,9- diethyl -3,9- dihydroxymethyl -1,5,7,11- tetra- oxygen spiral shells [5,
5] hendecane is to be added in three-necked flask by a certain amount of trimethylolpropane, adds dichloromethane, adds pyridine catalysis
Stirring is opened in agent, makes trimethylolpropane dissolving in organic solvent, the two phenoxy group dichloromethane dissolved with dichloromethane incline
It pours into dropping funel, is fixed on the branch mouth of three-necked flask, install blender, open dropping funel, make two phenoxy groups two
Chloromethanes is slowly dropped in trimethylolpropane solution, drips unsuitable too fast, the solution after two phenoxy group dichloromethane drip off of speed
It in purple, is poured into beaker, is washed with distilled water in batches, separate lower layer's organic solution.Organic layer is in finally after washing
It is existing faint yellow.By obtained yellow solution to get；The two phenoxy groups dichloromethane is to be equipped with blender, thermometer
With a certain amount of dried diphenyl carbonate is added in the three-necked flask of condenser pipe, connect tail gas receiving device；Open blender
After condensed water, it is slowly heated three-necked flask with temperature-controlled heating mantle, so that solid diphenyl carbonate is slowly molten into liquid, works as carbon
After diphenyl phthalate is completely melt, controls at 60 DEG C, divide 3 ~ 4 batches and a certain amount of phosphorus pentachloride is added into three-necked flask, it is to be added
Phosphorus pentachloride adds next group after being all dissolved in reaction solution, continuous heating makes temperature rise, and properly increases stirring speed
Degree, with the rising of temperature, slowly there is slightly boiling phenomenon in solution, and when temperature no longer rises, flow back 1h at this temperature, makes anti-
It should carry out more abundant, after finally allowing reaction solution to naturally cool to 30 DEG C, the dichloromethane that 300mL is added dissolves to get two
Phenoxy group dichloromethane.
Further, the foaming agent is 4,4'- oxobenzenesulfonyl hydrazide, dichlorotetra-fluoroethane, chlorotrifluoropropylene
It is one or more.
Further, the organic siliconresin modified epoxy is, by 67 parts of diphenyl dichlorosilane, dimethyl dichloro
13 parts of silane, 7.3 parts of boric acid are added in glass reactor；It is stirred continuously under nitrogen gas protection, and controls temperature 85 ~ 90
DEG C reaction 70min, is then added dropwise the solution of 8.5 parts of preparations of 3.8 parts of hydroquinone and normal propyl alcohol；After dripping, in 90 DEG C of constant temperature
95min is reacted, finally with 15 parts of methanol dilutions, up to organic siliconresin modified epoxy.
Further, the modified bismaleimide is by the reaction kettle equipped with blender, thermometer, being added two
50 parts of phenylmethane bismaleimide and 4 parts of cyanurate, 50 parts of solvent DMF, 0.1 part of triethylene tetramine, in temperature 110 DEG C ~ 140
After DEG C reaction lh, cooling be added the stirring of 50 parts of epoxy resin to get.
Further, the high-temperature-resistant epoxy resin be polyfunctional epoxy resin, specially trifunctional base epoxy,
DCPD modified epoxies, tetramethyl biphenyl epoxy resin, biphenyl epoxy resin and one kind or several in naphthalene nucleus epoxy resin
Kind.
Beneficial effects of the present invention：
The expansion requirements of adhesive volume are completed at a certain temperature, and also relate to adhesive solidification temperature range.Consider
Between Expanding Monomer open loop expansion temperature range the problems such as being mutually matched, can just obtain good performance.
The addition of high-temperature-resistant epoxy resin can not only improve adhesive heat resistance but also also improve cutting for adhesive
Shearing stress, ordinary epoxy resin is due to crosslink density height, and room temperature shear strength is relatively low, and epoxy-capped high tenacity resin has reached
To decomposition temperature, adhesive overall structure is decomposed, and shear strength is greatly reduced, this is because toughened resin heat resistance
Caused by difference.It is modified in adhesive using Expanding Monomer and certain Expanding Monomers is added, adhesive can be made in solidification process
Middle generation volume expansion overcomes the system of adhesive itself to shrink, to reach constancy of volume, can both keep good toughness,
Low water absorbable, and maintain good chemical-resistant, dimensional stability etc..
The present invention has the following advantages compared with prior art：
High-performance room-temperature solidification sticks agent and uses high activity polyfunctional epoxy resin and curing agent, cures in ambient cross-linking, to have
There is certain adhesive strength, but room temperature often cures not exclusively, therefore polyfunctional epoxy resin is added, but usually multifunctional ring
Oxygen resin activity is relatively low, therefore cures not exclusively, forms the oligomer of certain crosslink density, can be played in adhesive
Certain toughening effect, with the extension of hardening time and during applied at elevated temperature, polyfunctional epoxy resin is further solid
Change, crosslink density increases, and the high-temperature heat-resistance performance of adhesive is made to be improved.Under by external force destruction, effectively inhale
Extraneous energy of rupture is received, structural adhesive use is can be used as.Make the active hydrogen and bismaleimide of triethylene tetramine under high temperature
(BMI) addition reaction occurs for double bond, since there are span structures in curing agent, then coordinates tertiary amine as curing agent, further carries
The high heat resistance and curing reaction speed of curing agent, the high-performance room-temperature that can be prepared into Good Heat-resistance cure resistance to height
Temperature epoxy resin curing agent.It requires that a small amount of toughener is added in high-performance epoxy resin adhesive preparation process, so that it may to obtain
Good flexibility is obtained, but toughener dosage is excessive, often declines adhesive cohesive strength and heat resistance.But because of gradient
Toughening, is firstly added the resin of bifunctional high molecular weight in the epoxy, then adds rubber toughener, this gluing
When being acted on by external world, energy of rupture can be transmitted by gradient for agent, and constantly be absorbed, therefore more than direct toughening effect
It is good.The adhesive being prepared can not only obtain good toughness, and cohesive strength also declines seldom, and with good
Processing performance.
Specific implementation mode
Illustrate the present invention with specific embodiment below, but is not limitation of the present invention.
Embodiment 1
A kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat adhesive, is made of following component：Liquid end carboxyl butyronitrile rubber
15 ~ 20 parts of glue, 90 ~ 100 parts of epoxy resin, 90 ~ 100 parts of high-temperature-resistant epoxy resin, 20 ~ 30 parts of modifying epoxy resin by organosilicon,
8 ~ 12 parts of polyetheramine：8 ~ 12 parts of m-phenylene diamine (MPD), 20 ~ 25 parts of 4,4- diaminodiphenylmethane, 5 ~ 7 parts of amine terminated polyether, mica powder 6
~ 9 parts, 13 ~ 17 parts of flake asbestos, 60 ~ 80 parts of phenolic resin micro mist.
A kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat adhesive, preparation method includes the following steps：（1）Group
Divide the preparation of A：Each substance first is weighed with parts by weight by above-mentioned formula, by liquid nbr carboxyl terminal, epoxy resin, resistance to height
Temperature epoxy resin, is mixed into blender modifying epoxy resin by organosilicon, and modifying epoxy resin by organosilicon is first then put into three
It in mouth bottle, is warming up to 110 DEG C and keeps the temperature 1h, remove the solvent in modifying epoxy resin by organosilicon, then other each substances are added to
It in there-necked flask, stirs evenly, the liquid for making stable is component A；
（2）The preparation of component B：10 parts of polyetheramine, 10 parts of m-phenylene diamine (MPD), 23 parts of 4,4- diaminodiphenylmethane, amine terminated polyether 6
Part, each substance is sufficiently mixed and stirs evenly to get component B at a temperature of 50 ~ 60 DEG C；
（3）The preparation of component C：By mica powder, flake asbestos, phenolic resin micro mist through crushing, sieves, after compounding, it is single that expansion is added
50 parts of body is sufficiently mixed uniformly.With the working life after glue, the proportioning of adhesive is generally between 4 ~ 5h：First component：Second
Component：Third component=5：1：4,25 ~ 35 DEG C of solidification temperature.
Further, the Expanding Monomer be two phenoxy group dichloromethane and 3,9- diethyl -3,9- dihydroxymethyls -1,5,
7,11- tetra- oxygen spiral shell [5,5] undecanoic mixtures；3,9- diethyl -3,9- dihydroxymethyl -1,5,7,11- tetra- oxygen spiral shells [5,
5] hendecane is to be added in three-necked flask by a certain amount of trimethylolpropane, adds dichloromethane, adds pyridine catalysis
Stirring is opened in agent, makes trimethylolpropane dissolving in organic solvent, the two phenoxy group dichloromethane dissolved with dichloromethane incline
It pours into dropping funel, is fixed on the branch mouth of three-necked flask, install blender, open dropping funel, make two phenoxy groups two
Chloromethanes is slowly dropped in trimethylolpropane solution, drips unsuitable too fast, the solution after two phenoxy group dichloromethane drip off of speed
It in purple, is poured into beaker, is washed with distilled water in batches, separate lower layer's organic solution.Organic layer is in finally after washing
It is existing faint yellow.By obtained yellow solution to get；The two phenoxy groups dichloromethane is to be equipped with blender, thermometer
With a certain amount of dried diphenyl carbonate is added in the three-necked flask of condenser pipe, connect tail gas receiving device；Open blender
After condensed water, it is slowly heated three-necked flask with temperature-controlled heating mantle, so that solid diphenyl carbonate is slowly molten into liquid, works as carbon
After diphenyl phthalate is completely melt, controls at 60 DEG C, divide 3 ~ 4 batches and a certain amount of phosphorus pentachloride is added into three-necked flask, it is to be added
Phosphorus pentachloride adds next group after being all dissolved in reaction solution, continuous heating makes temperature rise, and properly increases stirring speed
Degree, with the rising of temperature, slowly there is slightly boiling phenomenon in solution, and when temperature no longer rises, flow back 1h at this temperature, makes anti-
It should carry out more abundant, after finally allowing reaction solution to naturally cool to 30 DEG C, the dichloromethane that 300mL is added dissolves to get two
Phenoxy group dichloromethane.
Further, the foaming agent is 4,4'- oxobenzenesulfonyl hydrazide, dichlorotetra-fluoroethane, chlorotrifluoropropylene
It is one or more.
Further, the organic siliconresin modified epoxy is, by 67 parts of diphenyl dichlorosilane, dimethyl dichloro
13 parts of silane, 7.3 parts of boric acid are added in glass reactor；It is stirred continuously under nitrogen gas protection, and controls temperature 85 ~ 90
DEG C reaction 70min, is then added dropwise the solution of 8.5 parts of preparations of 3.8 parts of hydroquinone and normal propyl alcohol；After dripping, in 90 DEG C of constant temperature
95min is reacted, finally with 15 parts of methanol dilutions, up to organic siliconresin modified epoxy.
Further, the modified bismaleimide is by the reaction kettle equipped with blender, thermometer, being added two
50 parts of phenylmethane bismaleimide and 4 parts of cyanurate, 50 parts of solvent DMF, 0.1 part of triethylene tetramine, in temperature 110 DEG C ~ 140
After DEG C reaction lh, cooling be added the stirring of 50 parts of epoxy resin to get.
Further, the high-temperature-resistant epoxy resin be polyfunctional epoxy resin, specially trifunctional base epoxy,
DCPD modified epoxies, tetramethyl biphenyl epoxy resin, biphenyl epoxy resin and one kind or several in naphthalene nucleus epoxy resin
Kind.
Embodiment 2
A kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat adhesive, is made of following component：Liquid end carboxyl butyronitrile rubber
15 ~ 20 parts of glue, 90 ~ 100 parts of epoxy resin, 90 ~ 100 parts of high-temperature-resistant epoxy resin, 20 ~ 30 parts of modifying epoxy resin by organosilicon,
8 ~ 12 parts of polyetheramine：8 ~ 12 parts of m-phenylene diamine (MPD), 20 ~ 25 parts of 4,4- diaminodiphenylmethane, 5 ~ 7 parts of amine terminated polyether, mica powder 6
~ 9 parts, 13 ~ 17 parts of flake asbestos, 60 ~ 80 parts of phenolic resin micro mist.
A kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat adhesive, preparation method includes the following steps：（1）Group
Divide the preparation of A：Each substance first is weighed with parts by weight by above-mentioned formula, by liquid nbr carboxyl terminal, epoxy resin, resistance to height
Temperature epoxy resin, is mixed into blender modifying epoxy resin by organosilicon, and modifying epoxy resin by organosilicon is first then put into three
It in mouth bottle, is warming up to 110 DEG C and keeps the temperature 1h, remove the solvent in modifying epoxy resin by organosilicon, then other each substances are added to
It in there-necked flask, stirs evenly, the liquid for making stable is component A；
（2）The preparation of component B：10 parts of polyetheramine, 10 parts of m-phenylene diamine (MPD), 23 parts of 4,4- diaminodiphenylmethane, amine terminated polyether 6
Part, each substance is sufficiently mixed and stirs evenly to get component B at a temperature of 50 ~ 60 DEG C；
（3）The preparation of component C：By mica powder, flake asbestos, phenolic resin micro mist through crushing, sieves, after compounding, it is single that expansion is added
50 parts of body is sufficiently mixed uniformly.With the working life after glue, the proportioning of adhesive is generally between 4 ~ 5h：First component：Second
Component：Third component=5：1：4,25 ~ 35 DEG C of solidification temperature.
Further, the Expanding Monomer be two phenoxy group dichloromethane and 3,9- diethyl -3,9- dihydroxymethyls -1,5,
7,11- tetra- oxygen spiral shell [5,5] undecanoic mixtures；3,9- diethyl -3,9- dihydroxymethyl -1,5,7,11- tetra- oxygen spiral shells [5,
5] hendecane is to be added in three-necked flask by a certain amount of trimethylolpropane, adds dichloromethane, adds pyridine catalysis
Stirring is opened in agent, makes trimethylolpropane dissolving in organic solvent, the two phenoxy group dichloromethane dissolved with dichloromethane incline
It pours into dropping funel, is fixed on the branch mouth of three-necked flask, install blender, open dropping funel, make two phenoxy groups two
Chloromethanes is slowly dropped in trimethylolpropane solution, drips unsuitable too fast, the solution after two phenoxy group dichloromethane drip off of speed
It in purple, is poured into beaker, is washed with distilled water in batches, separate lower layer's organic solution.Organic layer is in finally after washing
It is existing faint yellow.By obtained yellow solution to get；The two phenoxy groups dichloromethane is to be equipped with blender, thermometer
With a certain amount of dried diphenyl carbonate is added in the three-necked flask of condenser pipe, connect tail gas receiving device；Open blender
After condensed water, it is slowly heated three-necked flask with temperature-controlled heating mantle, so that solid diphenyl carbonate is slowly molten into liquid, works as carbon
After diphenyl phthalate is completely melt, controls at 60 DEG C, divide 3 ~ 4 batches and a certain amount of phosphorus pentachloride is added into three-necked flask, it is to be added
Phosphorus pentachloride adds next group after being all dissolved in reaction solution, continuous heating makes temperature rise, and properly increases stirring speed
Degree, with the rising of temperature, slowly there is slightly boiling phenomenon in solution, and when temperature no longer rises, flow back 1h at this temperature, makes anti-
It should carry out more abundant, after finally allowing reaction solution to naturally cool to 30 DEG C, the dichloromethane that 300mL is added dissolves to get two
Phenoxy group dichloromethane.
Further, the foaming agent is 4,4'- oxobenzenesulfonyl hydrazide, dichlorotetra-fluoroethane, chlorotrifluoropropylene
It is one or more.
Further, the organic siliconresin modified epoxy is, by 67 parts of diphenyl dichlorosilane, dimethyl dichloro
13 parts of silane, 7.3 parts of boric acid are added in glass reactor；It is stirred continuously under nitrogen gas protection, and controls temperature 85 ~ 90
DEG C reaction 70min, is then added dropwise the solution of 8.5 parts of preparations of 3.8 parts of hydroquinone and normal propyl alcohol；After dripping, in 90 DEG C of constant temperature
95min is reacted, finally with 15 parts of methanol dilutions, up to organic siliconresin modified epoxy comparative example 1
Further, the modified bismaleimide is by the reaction kettle equipped with blender, thermometer, being added hexichol first
50 parts of alkane bismaleimide and 4 parts of cyanurate, 50 parts of solvent DMF, 0.1 part of triethylene tetramine, it is anti-in 110 DEG C ~ 140 DEG C of temperature
After answering lh, cooling be added the stirring of 50 parts of epoxy resin to get.
Further, the high-temperature-resistant epoxy resin be polyfunctional epoxy resin, specially trifunctional base epoxy,
DCPD modified epoxies, tetramethyl biphenyl epoxy resin, biphenyl epoxy resin and one kind or several in naphthalene nucleus epoxy resin
Kind.
This comparative example compared with Example 2, in raw material weighs step, is saved liquid nbr carboxyl terminal ingredient, is removed
In addition method and step all same.
Comparative example 2
This comparative example compared with Example 2, in raw material weighs step, saves modified bismaleimide ingredient, in addition to this
Method and step all same.
Comparative example 3
This comparative example compared with Example 2, in raw material weighs step, saves Expanding Monomer ingredient, method and step in addition to this
All same.
The adhesive performance comparison of 1 embodiment and comparative example of table
The above is only a preferred embodiment of the present invention, it is noted that those skilled in the art are come
It says, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should be regarded as
Protection scope of the present invention.
Claims (7)
1. a kind of near-zero thermal expansion high-performance room-temperature cures inflatable boat adhesive, which is characterized in that be made of following component：Liquid
15 ~ 20 parts of nbr carboxyl terminal, 90 ~ 100 parts of epoxy resin, 90 ~ 100 parts of high-temperature-resistant epoxy resin, silicon-modified epoxy
20 ~ 30 parts of resin, 8 ~ 12 parts of polyetheramine：8 ~ 12 parts of m-phenylene diamine (MPD), 20 ~ 25 parts of 4,4- diaminodiphenylmethane, amine terminated polyether 5
~ 7 parts, 6 ~ 9 parts of mica powder, 13 ~ 17 parts of flake asbestos, 60 ~ 80 parts of phenolic resin micro mist.
2. a kind of near-zero thermal expansion high-performance room-temperature according to claim 1 cures inflatable boat adhesive, which is characterized in that
Preparation method includes the following steps：Specific preparation method is as follows：
（1）The preparation of component A：Each substance first is weighed with parts by weight by above-mentioned formula, by liquid nbr carboxyl terminal, epoxy
Resin, modifying epoxy resin by organosilicon, is mixed into blender high-temperature-resistant epoxy resin, then by silicon-modified epoxy tree
Fat is first put into there-necked flask, is warming up to 110 DEG C and is kept the temperature 1h, remove modifying epoxy resin by organosilicon in solvent, then by other
Each substance is added in there-necked flask, is stirred evenly, and the liquid for making stable is component A；
（2）The preparation of component B：10 parts of polyetheramine, 10 parts of m-phenylene diamine (MPD), 23 parts of 4,4- diaminodiphenylmethane, amine terminated polyether 6
Part, each substance is sufficiently mixed and stirs evenly to get component B at a temperature of 50 ~ 60 DEG C；
（3 ）The preparation of component C：By mica powder, flake asbestos, phenolic resin micro mist through crushing, sieves, after compounding, it is single that expansion is added
50 parts of body is sufficiently mixed uniformly.With the working life after glue, the proportioning of adhesive is generally between 4 ~ 5h：First component：Second
Component：Third component=5：1：4,25 ~ 35 DEG C of solidification temperature.
3. a kind of near-zero thermal expansion high-performance room-temperature according to claim 1 cures inflatable boat adhesive, which is characterized in that
The Expanding Monomer is two phenoxy group dichloromethane and 3,9- diethyl -3,9- dihydroxymethyls -1,5,7,11- tetra- oxygen spiral shells [5,5]
Undecanoic mixture；3,9- diethyl -3,9- dihydroxymethyl -1,5,7,11- tetra- oxygen spiral shell [5,5] hendecanes are by certain
Amount trimethylolpropane is added in three-necked flask, adds dichloromethane, adds pyridine catalyst, is opened stirring, is made three
Hydroxymethyl-propane dissolves in organic solvent, and the two phenoxy group dichloromethane dissolved with dichloromethane are poured into dropping funel,
It is fixed on the branch mouth of three-necked flask, installs blender, open dropping funel, two phenoxy group dichloromethane is made to be slowly dropped to
In trimethylolpropane solution, dripping speed should not be too fast, and solution is in purple after two phenoxy group dichloromethane drip off, and is poured into beaker
In, it is washed with distilled water in batches, separates lower layer's organic solution.Organic layer is finally presented faint yellow after washing.By what is obtained
Yellow solution to get；The two phenoxy groups dichloromethane is in the three-necked flask for being equipped with blender, thermometer and condenser pipe
It is middle that a certain amount of dried diphenyl carbonate is added, connect tail gas receiving device；After opening blender and condensed water, with temperature control plus
Hot jacket is slowly heated three-necked flask, and solid diphenyl carbonate is made slowly to be molten into liquid, after diphenyl carbonate is completely melt,
Control divides 3 ~ 4 batches and a certain amount of phosphorus pentachloride is added into three-necked flask, phosphorus pentachloride to be added is all dissolved in instead at 60 DEG C
Next group is added after answering in liquid, continuous heating makes temperature rise, and properly increases mixing speed, molten with the rising of temperature
Slowly there is slightly boiling phenomenon in liquid, and when temperature no longer rises, flow back 1h at this temperature, so that reaction is carried out more abundant, most
After allow reaction solution to naturally cool to 30 DEG C after, be added 300mL dichloromethane dissolve to get two phenoxy group dichloromethane.
4. a kind of near-zero thermal expansion high-performance room-temperature according to claim 1 cures inflatable boat adhesive, which is characterized in that
The foaming agent be 4,4'- oxobenzenesulfonyl hydrazide, dichlorotetra-fluoroethane, chlorotrifluoropropylene it is one or more.
5. a kind of near-zero thermal expansion high-performance room-temperature according to claim 1 cures inflatable boat adhesive, which is characterized in that
The organic siliconresin modified epoxy is, by 67 parts of diphenyl dichlorosilane, 13 parts of dimethyldichlorosilane, boric acid 7.3
Part is added in glass reactor；It is stirred continuously under nitrogen gas protection, and controls temperature and react 70min at 85 ~ 90 DEG C, then
The solution of 8.5 parts of preparations of 3.8 parts of hydroquinone and normal propyl alcohol is added dropwise；After dripping, in 90 DEG C of constant temperature 95min, reacted, most
Afterwards with 15 parts of methanol dilutions, up to organic siliconresin modified epoxy.
6. a kind of near-zero thermal expansion high-performance room-temperature according to claim 1 cures inflatable boat adhesive, which is characterized in that
The modified bismaleimide is by the reaction kettle equipped with blender, thermometer, being added diphenyl-methane bismaleimide
50 parts of amine and 4 parts of cyanurate, 50 parts of solvent DMF, 0.1 part of triethylene tetramine, after 110 DEG C ~ 140 DEG C reaction lh of temperature, cooling
Be added the stirring of 50 parts of epoxy resin to get.
7. a kind of near-zero thermal expansion high-performance room-temperature according to claim 1 cures inflatable boat adhesive, which is characterized in that
The high-temperature-resistant epoxy resin be polyfunctional epoxy resin, specially trifunctional base epoxy, DCPD modified epoxies,
One or more of tetramethyl biphenyl epoxy resin, biphenyl epoxy resin and naphthalene nucleus epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810641072.2A CN108753229A (en) | 2018-06-21 | 2018-06-21 | A kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810641072.2A CN108753229A (en) | 2018-06-21 | 2018-06-21 | A kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108753229A true CN108753229A (en) | 2018-11-06 |
Family
ID=63979422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810641072.2A Withdrawn CN108753229A (en) | 2018-06-21 | 2018-06-21 | A kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108753229A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019576A (en) * | 2019-11-22 | 2020-04-17 | 南京工程学院 | Aromatic bismaleimide modified liquid polysulfide rubber toughened epoxy adhesive and preparation method thereof |
| CN115449324A (en) * | 2022-09-15 | 2022-12-09 | 朋诺惠利电子材料(厦门)有限公司 | High-strength single-component epoxy adhesive composition and preparation method thereof |
| CN116004183A (en) * | 2023-02-02 | 2023-04-25 | 江苏晶河电子科技有限公司 | High-temperature-resistant adhesive for microelectronic device and preparation method thereof |
-
2018
- 2018-06-21 CN CN201810641072.2A patent/CN108753229A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019576A (en) * | 2019-11-22 | 2020-04-17 | 南京工程学院 | Aromatic bismaleimide modified liquid polysulfide rubber toughened epoxy adhesive and preparation method thereof |
| CN111019576B (en) * | 2019-11-22 | 2021-08-10 | 南京工程学院 | Aromatic bismaleimide modified liquid polysulfide rubber toughened epoxy adhesive and preparation method thereof |
| CN115449324A (en) * | 2022-09-15 | 2022-12-09 | 朋诺惠利电子材料(厦门)有限公司 | High-strength single-component epoxy adhesive composition and preparation method thereof |
| CN116004183A (en) * | 2023-02-02 | 2023-04-25 | 江苏晶河电子科技有限公司 | High-temperature-resistant adhesive for microelectronic device and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108753229A (en) | A kind of near-zero thermal expansion high-performance room-temperature solidification inflatable boat adhesive | |
| CN105906842A (en) | Modified graphene oxide and epoxy resin composite material and method for preparing same | |
| JPS6221803B2 (en) | ||
| CN101407708A (en) | High temperature resistant, high strength modified epoxy resin adhesive and preparation thereof | |
| CN101186796A (en) | Method for preparing epoxy resin adhesive | |
| CN104045810A (en) | Diamine addition crosslinking agent and preparation method thereof, as well as composition for preparing thermal reversible crosslinking epoxy resin and composite material of thermal reversible crosslinking epoxy resin | |
| CN108997560A (en) | A kind of epoxy resin composite material and its preparation method and application | |
| CN104449552A (en) | Adhesive mono-component addition silicone rubber adhesive and preparation method thereof | |
| CN111004472B (en) | Epoxy resin prepolymer with phase-splitting structure and preparation method and application thereof | |
| CN108102097A (en) | A kind of polyimides of base containing benzyne, preparation method and applications | |
| CN101487190B (en) | Polyimide carbon fiber sizing agent and method for producing the same | |
| CN105061764B (en) | A kind of thermoset polyimide resin and its composite laminate and their preparation method and application | |
| CN107129493A (en) | A kind of two amine type bi-benzoxazines of the imide containing alicyclic and preparation method thereof | |
| CN103131181A (en) | Toughened cyanate resin and preparation method thereof | |
| CN101824157A (en) | Method for modifying cyanate ester resin by hydroxyl-terminated polybutadiene | |
| CN101544807B (en) | Epoxy anti-fouling material and preparation method and use of same | |
| CN105400476B (en) | A kind of modified lignin resin polyamic acid/epoxy resin composite adhesive and preparation method thereof | |
| CN101735573A (en) | Modified epoxy resin film for RFI molding process and preparation method thereof | |
| CN109385241A (en) | A kind of silicon Graft Epoxy Resin adhesive | |
| CN111875793A (en) | Phthalonitrile resin for composite material and preparation method thereof | |
| CN110498923A (en) | A kind of easily molded polyimide resin of superhigh temperature resistant and the preparation method and application thereof | |
| CN108865048A (en) | A kind of preparation method of high viscosity polyimides adhesive new material | |
| CN109503520A (en) | 5- aldehyde radical resorcinolformaldehyde resin and preparation method thereof | |
| CN1233768C (en) | Epoxy resin adhesive containing dimalea mic and preparation process thereof | |
| CN109233710A (en) | Insulating material with high glass transition temperature and high-temperature cohesiveness and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20181106 |
|
| WW01 | Invention patent application withdrawn after publication |