CN109486457A - A kind of high temperature resistant height glues high-strength and high ductility interlaminar bonding material and preparation method - Google Patents
A kind of high temperature resistant height glues high-strength and high ductility interlaminar bonding material and preparation method Download PDFInfo
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- CN109486457A CN109486457A CN201811219012.8A CN201811219012A CN109486457A CN 109486457 A CN109486457 A CN 109486457A CN 201811219012 A CN201811219012 A CN 201811219012A CN 109486457 A CN109486457 A CN 109486457A
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- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention discloses a kind of high temperature resistant height to glue high-strength and high ductility interlaminar bonding material and preparation method, the interlaminar bonding material based on parts by weight, is prepared from the following raw materials: 15~20 parts of polytetrahydrofuran ether glycol, 5~10 parts of isophorone diisocyanate, 5~10 parts of succinic anhydride, 5~10 parts of diethanol amine, 4~8 parts of trimethylolpropane, 30~40 parts of Heterocyclic Aramid Fibre, 100 parts of epoxy resin, 10~15 parts of polyethylene polyamine.The preparation method of the interlaminar bonding material is to prepare aliphatic super branched polyurethane, obtain interlaminar bonding material to Heterocyclic Aramid Fibre surface treatment, the curing agent for carrying out surface grafting processing to Heterocyclic Aramid Fibre, the modified Heterocyclic Aramid Fibre epoxy curing agent of super branched polyurethane being prepared by the modified Heterocyclic Aramid Fibre of super branched polyurethane and epoxy resin, adds preparation into epoxy resin.Interlaminar bonding material of the invention has the excellent properties such as high intensity, high tenacity, shock resistance, and preparation process is simple, reaction process is controllable.
Description
Technical field
The invention belongs to pavement material fields, are related to a kind of interlaminar bonding material, and in particular to a kind of viscous height of high temperature resistant height
Strong high-ductility interlaminar bonding material and preparation method.
Background technique
Deck paving bonding damage layer is a main cause for leading to deck paving disease, the quality of deck paving bonding
Directly affect the safety of driving, the service life of comfort or even bridge；Pave-load layer can be improved in good water-proof tack coat
Anti-shear performance, reduce pave-load layer and generate passage, gather around the early diseases such as packet, infiltration and happen.Epoxy resin has excellent
Adhesive property and the advantages that good high-modulus, high intensity, chemical resistance, epoxy is at home and abroad found in chronic study procedure
Resin bridge deck water-proof, in terms of have and apparent advantage and be used widely.But with overload, heavily loaded normality
Change is put forward higher requirements to waterproof binding material and epoxy resin the shortcomings that there are brittleness is big and poor impact resistance itself,
Therefore it need to be subject to toughening enhancing to epoxy resin and make it have superior performance.
Summary of the invention
For the defects in the prior art and insufficient, the present invention provides a kind of high temperature resistant height to glue high-strength and high ductility interlaminar bonding
Material and preparation method overcome the defect that existing binding material toughness is low, impact resistance is poor.
In order to achieve the above objectives, the invention adopts the following technical scheme:
A kind of viscous high-strength and high ductility interlaminar bonding material of high temperature resistant height, the raw material for preparing the binding material includes epoxy resin,
It further include polytetrahydrofuran ether glycol, isophorone diisocyanate, succinic anhydride, diethanol amine, trimethylolpropane, heterocycle
Aramid fiber and polyethylene polyamine.
Based on parts by weight, it is prepared from the following raw materials: 15~20 parts of polytetrahydrofuran ether glycol (PTMG), isophorone
5~10 parts of diisocyanate (IP-DI), 5~10 parts of succinic anhydride, 5~10 parts of diethanol amine, 4~8 parts of trimethylolpropane,
30~40 parts of Heterocyclic Aramid Fibre, 100 parts of epoxy resin, 10~15 parts of polyethylene polyamine.
The present invention also has following technical characteristic:
Optionally, based on parts by weight, it is prepared from the following raw materials: 15~20 parts of polytetrahydrofuran ether glycol, isophorone
5~10 parts of diisocyanate, 5~8 parts of succinic anhydride, 5~8 parts of diethanol amine, 4~6 parts of trimethylolpropane, heterocycle aramid fiber are fine
Tie up 35 parts, 100 parts of epoxy resin, 12 parts of polyethylene polyamine.
Optionally, based on parts by weight, be prepared from the following raw materials: 18 parts of polytetrahydrofuran ether glycol, isophorone two are different
7 parts of cyanate, 7 parts of succinic anhydride, 8 parts of diethanol amine, 5 parts of trimethylolpropane, 35 parts of Heterocyclic Aramid Fibre, epoxy resin
100 parts, 12 parts of polyethylene polyamine.
Optionally, the structural formula of the Heterocyclic Aramid Fibre are as follows:
Wherein: n value range is 100~1000.
It is 2,5- Diaminothiazoles and terephthalic acid (TPA) that the Heterocyclic Aramid Fibre, which is a kind of initial monomers, passes through high temperature
A kind of 5-member heterocyclic ring containing nitrogen Nomex of solution polymerization process synthesis, can be dissolved in dimethyl sulfoxide and n,N-Dimethylformamide
Equal organic solvents, fusing point are greater than 310 DEG C.
Optionally, the epoxy resin is bisphenol A type epoxy resin E-44, wherein bisphenol A type epoxy resin E-44's
Epoxide number is 0.41~0.47eq/100g, epoxide equivalent is 212~244g/eq.
Optionally, the polyethylene polyamine is any one in diethylenetriamine, triethylene tetramine or tetraethylenepentamine
Or it is a variety of compound.
In the present invention, the molecular weight Mn=1000 of polytetrahydrofuran ether glycol, polymerization degree n=13.6.
The present invention also provides the preparation method that a kind of high temperature resistant height glues high-strength and high ductility interlaminar bonding material, the preparation methods
The raw material of high-strength and high ductility interlaminar bonding material is glued using the high temperature resistant height, method includes the following steps:
Step 1: preparation aliphatic super branched polyurethane:
Using n,N-Dimethylformamide (DMF) as solvent, the polytetrahydrofuran ether glycol after drying is added, using February
Dilaurylate is catalyst, and isophorone diisocyanate is added dropwise and reacts 1.5h in nitrogen atmosphere at 75 DEG C, obtains
To the base polyurethane prepolymer for use as (PPU) of-NCO sealing end；
With methanol as solvent, succinic anhydride and diethanol amine are added under ice-water bath, reacts 6h in nitrogen atmosphere, dry
4- (bis- (2- ethoxy) imines) -4- ketobutyric acid (AB2) monomer；Continue trimethylolpropane and above-mentioned 4- (bis- (2- hydroxyl second
Base) imines) -4- ketobutyric acid (AB2) monomer is added in reaction kettle, makees catalyst with toluenesulfonic acid, and toluene is water entrainer,
For esterification 8h to anhydrous generation, obtaining faint yellow thick liquid is dissaving polymer (HPAE) at 120 DEG C；
The dissaving polymer HPAE of preparation is added in the above-mentioned base polyurethane prepolymer for use as (PPU) prepared, in nitrogen gas
In atmosphere, 4.5h is reacted at 75 DEG C, obtaining colourless viscous liquid is aliphatic super branched polyurethane (HBPU)；
Step 2: Heterocyclic Aramid Fibre surface treatment:
It is dried after 400 mesh Heterocyclic Aramid Fibres are cleaned by ultrasonic 2h with acetone, then mass concentration is 20%, temperature is
It is impregnated in 40 DEG C of phosphoric acid solution, is dried in vacuo 12h at 80 DEG C after immersion, be then added to the molten of isophorone diisocyanate
It is reacted in liquid, spends Ion Cleaning and obtain hydroxyl-OH, isocyano that high activity is contained on surface to neutrality and after drying
The Heterocyclic Aramid Fibre of base-NCO and amino-NH2 surface treatment；
Step 3: the processing of Heterocyclic Aramid Fibre surface grafting:
The aliphatic super branched polyurethane (HBPU) of step 1 preparation is added in reaction kettle, with N, N- dimethyl formyl
Amine makees diluent, is added the surface treated Heterocyclic Aramid Fibre of above-mentioned steps two, through ultrasonication at 80~90 DEG C
Afterwards, it is reacted 5 hours under conditions of high speed shear and obtains the Heterocyclic Aramid Fibre of surface grafting super branched polyurethane, separated, mention
It is pure, dry that super branched polyurethane is modified Heterocyclic Aramid Fibre；
Step 4: the preparation of epoxy curing agent:
The modified Heterocyclic Aramid Fibre of super branched polyurethane obtained in step 3 and epoxy resin are dissolved in propylene glycol monomethyl ether
Afterwards, it is added in reaction kettle and reacts 3.5h at 70 DEG C with surfactant, add polyethylene polyamine and carry out addition reaction, add fourth
Base glycidol ether blocks addition product, is cooled to 50 DEG C of addition glacial acetic acid after reaction and adjusts hydrophile-lipophile balance,
Distilling off solvent is at reduced pressure conditions to get the modified Heterocyclic Aramid Fibre epoxy curing agent of super branched polyurethane；
Step 5: interlaminar bonding material is prepared:
It is solid that the modified Heterocyclic Aramid Fibre epoxy resin of the super branched polyurethane prepared in step 4 is added into epoxy resin
Agent, high-speed stirred, which is uniformly mixed, after ultrasonic disperse processing glues high-strength high-toughness epoxy to get to normal temperature solidified high temperature resistant height
Resin compounded interlaminar bonding material.
Specifically, the structural formula for the base polyurethane prepolymer for use as being prepared in step 1 are as follows:
The structural formula for the dissaving polymer being prepared in step 1 are as follows:
The structural formula for the aliphatic super branched polyurethane being prepared in step 1 are as follows:
Compared with prior art, the present invention beneficial has the technical effect that
(I) super branched polyurethane and polyethylene polyamine are used for Heterocyclic Aramid Fibre modification for the first time by the present invention simultaneously, for the first time
The modification Heterocyclic Aramid Fibre composite material of curable epoxy is made.
(II) Heterocyclic Aramid Fibre that the present invention uses is 2,5- Diaminothiazoles and terephthaldehyde for a kind of initial monomers
Acid, the kind 5-member heterocyclic ring containing nitrogen Nomex synthesized by high-temp. solution polymerization method, can be dissolved in dimethyl sulfoxide and N, N- bis-
The organic solvents such as methylformamide have excellent thermal stability, solubility property and mechanical property.
(III) present invention handles Heterocyclic Aramid Fibre using 20% phosphoric acid solution (mass concentration), can make fiber surface hydroxyl
The oxygen-containing functional groups quantity such as base-OH increases, and increases its activity.Continue to handle fiber using IP-DI solution, obtains surface and contain height
Hydroxyl-OH, isocyanate base-NCO and amino-NH2 fiber of activity connects for over-expense polyurethane and polyethylene polyamine
Branch creates advantageous condition.
(IV) super branched polyurethane that the present invention uses is made using graft copolymerization, in the base polyurethane prepolymer for use as molecule of straight chain
The Hyperbranched Polymer with Terminal Hydroxyl with branched structure is introduced on segment.The super branched polyurethane degree of branching is high, has elliposoidal knot
Structure, molecule have good mobility and dissolubility, reaction with a large amount of active function groups such as isocyanate base, methyl, hydroxyls
It is active high, on the Heterocyclic Aramid Fibre after capable of being successfully grafted to surface treated；Grafting super branched polyurethane can be obviously modified
Heterocyclic Aramid Fibre surface-active can effectively improve its adhesive effect between epoxy resin；And super branched polyurethane is with excellent
Flexibility and resistance to low temperature more are obvious for epoxy resin roughening effect.
(V) polyethylene polyamine is grafted to Heterocyclic Aramid Fibre and over-expense polyurethane surface and uses butyl by the present invention
Glycidol ether blocks addition product, and the polyurethane-modified Heterocyclic Aramid Fibre of over-expense of curable epoxy is made.
(VI) it can effectively improve ring through the modified Heterocyclic Aramid Fibre of super branched polyurethane in interlayer materials prepared by the present invention
The disadvantages of oxygen tree toughness is low and poor impact resistance, and polyethylene polyamine is grafted on modified Heterocyclic Aramid Fibre, make its with
While epoxy resin is physical crosslinking and epoxy resin generates the combination epoxy resin cure of chemical bond, fiber and asphalt mixtures modified by epoxy resin
Aliphatic radical body bond effect is excellent, and epoxy resin composite material pavement performance is obviously improved.
(VII) present invention prepares surface grafting super branched polyurethane using ultrasonication HBPU and Heterocyclic Aramid Fibre
Heterocyclic Aramid Fibre, and using the modified Heterocyclic Aramid Fibre epoxy curing agent of ultrasonication super branched polyurethane and ring
Oxygen resin prepares epoxy resin compoiste adhering material, is made it have using ultrasonication nanoscale Heterocyclic Aramid Fibre in machinery
The evenly dispersed and haptoreaction effect being unable to reach under stirring, so that over-expense polyurethane and Heterocyclic Aramid Fibre items superiority
Chemiluminescence is played while capable of being not fully exerted, the interlaminar bonding material haveing excellent performance is made.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Embodiment 1:
The present embodiment provides a kind of viscous high-strength and high ductility interlaminar bonding material of high temperature resistant height, based on parts by weight, by following original
Material is made: 15 parts of polytetrahydrofuran ether glycol (PTMG), 5 parts of isophorone diisocyanate (IP-DI), 5 parts of succinic anhydride, two
5 parts of ethanol amine, 4 parts of trimethylolpropane, 35 parts of Heterocyclic Aramid Fibre, 100 parts of epoxy resin, 12 parts of triethylene tetramine.
Heterocyclic Aramid Fibre in the present embodiment is 5-member heterocyclic ring containing nitrogen Nomex, specific structural formula are as follows:
Wherein: n value range is 100~1000.It is 2,5- diamino that the Heterocyclic Aramid Fibre, which is a kind of initial monomers,
Base thiazole and terephthalic acid (TPA), a kind of 5-member heterocyclic ring containing nitrogen Nomex synthesized by high-temp. solution polymerization method, can be dissolved in
The organic solvents such as dimethyl sulfoxide and n,N-Dimethylformamide, fusing point are greater than 310 DEG C.
Epoxy resin in the present embodiment is bisphenol A type epoxy resin E-44, the epoxy of bisphenol A type epoxy resin E-44
Value is 0.41~0.47eq/100g, epoxide equivalent is 212~244g/eq.
In the present embodiment, the molecular weight Mn=1000 of polytetrahydrofuran ether glycol, polymerization degree n=13.6.
The high temperature resistant height of the present embodiment glues the preparation method of high-strength and high ductility interlaminar bonding material, high using the high temperature resistant
The raw material of viscous high-strength and high ductility interlaminar bonding material, method includes the following steps:
Step 1: preparation aliphatic super branched polyurethane:
Using n,N-Dimethylformamide (DMF) as solvent, the polytetrahydrofuran ether glycol after drying is added, using February
Dilaurylate is catalyst, and isophorone diisocyanate is added dropwise and reacts 1.5h in nitrogen atmosphere at 75 DEG C, obtains
To the base polyurethane prepolymer for use as (PPU) of-NCO sealing end；
With methanol as solvent, succinic anhydride and diethanol amine are added under ice-water bath, reacts 6h in nitrogen atmosphere, dry
4- (bis- (2- ethoxy) imines) -4- ketobutyric acid (AB2) monomer；Continue trimethylolpropane and above-mentioned 4- (bis- (2- hydroxyl second
Base) imines) -4- ketobutyric acid (AB2) monomer is added in reaction kettle, makees catalyst with toluenesulfonic acid, and toluene is water entrainer,
For esterification 8h to anhydrous generation, obtaining faint yellow thick liquid is dissaving polymer (HPAE) at 120 DEG C；
The dissaving polymer HPAE of preparation is added in the above-mentioned base polyurethane prepolymer for use as (PPU) prepared, in nitrogen gas
In atmosphere, 4.5h is reacted at 75 DEG C, obtaining colourless viscous liquid is aliphatic super branched polyurethane (HBPU)；
Specifically, the structural formula for the base polyurethane prepolymer for use as being prepared in step 1 are as follows:
The structural formula for the dissaving polymer being prepared in step 1 are as follows:
The structural formula for the aliphatic super branched polyurethane being prepared in step 1 are as follows:
Wherein, dissaving polymer HPAE is added in base polyurethane prepolymer for use as (PPU), reaction process is as follows:
Step 2: Heterocyclic Aramid Fibre surface treatment:
It is dried after 400 mesh Heterocyclic Aramid Fibres are cleaned by ultrasonic 2h with acetone, then mass concentration is 20%, temperature is
It is impregnated in 40 DEG C of phosphoric acid solution, is dried in vacuo 12h at 80 DEG C after immersion, be then added to the molten of isophorone diisocyanate
It is reacted in liquid, spends Ion Cleaning and obtain hydroxyl-OH, isocyano that high activity is contained on surface to neutrality and after drying
The Heterocyclic Aramid Fibre of base-NCO and amino-NH2 surface treatment；
Step 3: the processing of Heterocyclic Aramid Fibre surface grafting:
The aliphatic super branched polyurethane (HBPU) of step 1 preparation is added in reaction kettle, with N, N- dimethyl formyl
Amine makees diluent, is added the surface treated Heterocyclic Aramid Fibre of above-mentioned steps two, through ultrasonication at 80~90 DEG C
Afterwards, it is reacted 5 hours under conditions of high speed shear and obtains the Heterocyclic Aramid Fibre of surface grafting super branched polyurethane, separated, mention
It is pure, dry that super branched polyurethane is modified Heterocyclic Aramid Fibre；
Step 4: the preparation of epoxy curing agent:
The modified Heterocyclic Aramid Fibre of super branched polyurethane obtained in step 3 and epoxy resin are dissolved in propylene glycol monomethyl ether
Afterwards, it is added in reaction kettle and reacts 3.5h at 70 DEG C with surfactant, add polyethylene polyamine and carry out addition reaction, add fourth
Base glycidol ether blocks addition product, is cooled to 50 DEG C of addition glacial acetic acid after reaction and adjusts hydrophile-lipophile balance,
Distilling off solvent is at reduced pressure conditions to get the modified Heterocyclic Aramid Fibre epoxy curing agent of super branched polyurethane；
Step 5: interlaminar bonding material is prepared:
It is solid that the modified Heterocyclic Aramid Fibre epoxy resin of the super branched polyurethane prepared in step 4 is added into epoxy resin
Agent, high-speed stirred, which is uniformly mixed, after ultrasonic disperse processing glues high-strength high-toughness epoxy to get to normal temperature solidified high temperature resistant height
Resin compounded interlaminar bonding material.
Embodiment 2:
The present embodiment provides a kind of viscous high-strength and high ductility interlaminar bonding material of high temperature resistant height, based on parts by weight, by following original
PTMG18 parts, IP-DI7 parts, 7 parts of succinic anhydride, 8 parts of diethanol amine, 5 parts of trimethylolpropane, heterocycle aramid fiber fibre is made in material
Tie up 35 parts, 100 parts of epoxy resin, 12 parts of triethylene tetramine.
The selection of raw material and specification are same as Example 1 in the present embodiment.
The preparation method that the high temperature resistant height of the present embodiment glues high-strength and high ductility interlaminar bonding material is identical as embodiment 1.
Embodiment 3:
The present embodiment provides a kind of viscous high-strength and high ductility interlaminar bonding material of high temperature resistant height, based on parts by weight, by following original
Material is made: PTMG20 parts, IP-DI10 parts, 10 parts of succinic anhydride, 10 parts of diethanol amine, 8 parts of trimethylolpropane, heterocycle virtue
35 parts of synthetic fibre fiber, 100 parts of epoxy resin, 12 parts of triethylene tetramine.
The selection of raw material and specification are same as Example 1 in the present embodiment.
The preparation method that the high temperature resistant height of the present embodiment glues high-strength and high ductility interlaminar bonding material is identical as embodiment 1.
Embodiment 4:
The present embodiment provides a kind of viscous high-strength and high ductility interlaminar bonding material of high temperature resistant height, based on parts by weight, by following original
Material is made: 18 parts of PTMG, 7 parts of IP-DI, 7 parts of succinic anhydride, 8 parts of diethanol amine, 5 parts of trimethylolpropane, heterocycle virtue
30 parts of synthetic fibre fiber, 100 parts of epoxy resin, 12 parts of triethylene tetramine.
The selection of raw material and specification are same as Example 1 in the present embodiment.
The preparation method that the high temperature resistant height of the present embodiment glues high-strength and high ductility interlaminar bonding material is identical as embodiment 1.
Embodiment 5:
The present embodiment provides a kind of viscous high-strength and high ductility interlaminar bonding material of high temperature resistant height, based on parts by weight, by following original
Material is made: 18 parts of PTMG, 7 parts of IP-DI, 7 parts of succinic anhydride, 8 parts of diethanol amine, 5 parts of trimethylolpropane, heterocycle virtue
40 parts of synthetic fibre fiber, 100 parts of epoxy resin, 12 parts of triethylene tetramine.
The selection of raw material and specification are same as Example 1 in the present embodiment.
The preparation method that the high temperature resistant height of the present embodiment glues high-strength and high ductility interlaminar bonding material is identical as embodiment 1.
Embodiment 6:
The present embodiment provides a kind of viscous high-strength and high ductility interlaminar bonding material of high temperature resistant height, based on parts by weight, by following original
Material is made: 18 parts of PTMG, 7 parts of IP-DI, 7 parts of succinic anhydride, 8 parts of diethanol amine, 5 parts of trimethylolpropane, heterocycle virtue
35 parts of synthetic fibre fiber, 100 parts of epoxy resin, 10 parts of triethylene tetramine.
The selection of raw material and specification are same as Example 1 in the present embodiment.
The preparation method that the high temperature resistant height of the present embodiment glues high-strength and high ductility interlaminar bonding material is identical as embodiment 1.
Embodiment 7:
The present embodiment provides a kind of viscous high-strength and high ductility interlaminar bonding material of high temperature resistant height, based on parts by weight, by following original
Material is made: 18 parts of PTMG, 7 parts of IP-DI, 7 parts of succinic anhydride, 8 parts of diethanol amine, 5 parts of trimethylolpropane, heterocycle virtue
35 parts of synthetic fibre fiber, 100 parts of epoxy resin, 15 parts of triethylene tetramine.
The selection of raw material and specification are same as Example 1 in the present embodiment.
The preparation method that the high temperature resistant height of the present embodiment glues high-strength and high ductility interlaminar bonding material is identical as embodiment 1.
Embodiment 8:
The present embodiment provides a kind of viscous high-strength and high ductility interlaminar bonding material of high temperature resistant height, based on parts by weight, by following original
Material is made: 15 parts of PTMG, 5 parts of IP-DI, 5 parts of succinic anhydride, 5 parts of diethanol amine, 5 parts of trimethylolpropane, heterocycle virtue
30 parts of synthetic fibre fiber, 100 parts of epoxy resin, 10 parts of triethylene tetramine.
The selection of raw material and specification are same as Example 1 in the present embodiment.
The preparation method that the high temperature resistant height of the present embodiment glues high-strength and high ductility interlaminar bonding material is identical as embodiment 1.
Embodiment 9:
The present embodiment provides a kind of viscous high-strength and high ductility interlaminar bonding material of high temperature resistant height, based on parts by weight, by following original
Material is made: 20 parts of PTMG, 10 parts of IP-DI, 10 parts of succinic anhydride, 10 parts of diethanol amine, 8 parts of trimethylolpropane, heterocycle
40 parts of aramid fiber, 100 parts of epoxy resin, 15 parts of triethylene tetramine.
The selection of raw material and specification are same as Example 1 in the present embodiment.
The preparation method that the high temperature resistant height of the present embodiment glues high-strength and high ductility interlaminar bonding material is identical as embodiment 1.
Comparative example 1:
This comparative example provides a kind of interlaminar bonding material, this comparative example difference from Example 2 is that epoxy resin is not
It is modified processing.
This comparative example based on parts by weight, is made of following raw material: epoxy resin bisphenol A type epoxy resin E-44 100
Part, 12 parts of triethylene tetramine.
Epoxy resin and triethylene tetramine used are same as Example 1 in this comparative example.
The preparation method of the interlaminar bonding material of this comparative example carries out in accordance with the following steps:
Triethylene tetramine is added into epoxy resin, high-speed stirred, which is uniformly mixed, after ultrasonic disperse processing obtains a kind of layer
Between binding material.
Comparative example 2:
This comparative example provides a kind of interlaminar bonding material, this comparative example difference from Example 2 is, only with over-expense
Change polyurethane to be modified epoxy resin.
This comparative example based on parts by weight, is made of following raw material: 18 parts of PTMG, 7 parts of IP-DI, succinic anhydride 7
Part, 8 parts of diethanol amine, 5 parts of trimethylolpropane, 100 parts of epoxy resin, 12 parts of triethylene tetramine.
The selection of raw material and specification are same as Example 1 in this comparison.
The preparation method of the interlaminar bonding material of this comparative example carries out in accordance with the following steps:
Step 1, according to the preparation method preparation over-expense polyurethane of the aliphatic over-expense polyurethane of embodiment 1.
Step 2, by epoxy resin, triethylene tetramine and super branched polyurethane, high-speed stirred is mixed after ultrasonic disperse processing
It closes and uniformly obtains a kind of interlaminar bonding material.
Comparative example 3:
This comparative example provides a kind of interlaminar bonding material, this comparative example difference from Example 2 is, only with heterocycle
Aramid fiber is modified epoxy resin.
This comparative example based on parts by weight, is made of following raw material: 35 parts of Heterocyclic Aramid Fibre, 100 parts of epoxy resin,
12 parts of triethylene tetramine.
The selection of raw material and specification are same as Example 1 in this comparative example.
The preparation method of the interlayer materials of this comparative example carries out in accordance with the following steps:
Step 1, Heterocyclic Aramid Fibre surface treatment.After 400 mesh Heterocyclic Aramid Fibres are cleaned by ultrasonic 2h with acetone, it is
Increase the phosphoric acid solution (mass concentration) of addition 20% after fiber surface oxygen-containing functional group content is baked to, impregnates one at 40 DEG C
It is taken out after fixing time, 12h is dried in vacuo at 80 DEG C, reaction certain time in IP-DI solution is added and takes out, it is clear with deionized water
It is washed till neutral and drying, obtains hydroxyl-OH, isocyanate base-NCO and amino-the NH2 fiber for containing high activity in surface.
Step 2, epoxy curing agent preparation.By above-mentioned Heterocyclic Aramid Fibre and epoxy resin bisphenol-A type asphalt mixtures modified by epoxy resin
Rouge E-44, which is dissolved in propylene glycol monomethyl ether and is added in reaction kettle, reacts 3.5h at 70 DEG C with surfactant, adds polyethylene polyamine
Addition reaction is carried out, addition butyl glycidyl ether blocks addition product, is cooled to 50 DEG C of addition ice vinegar after reaction
Acid adjusts hydrophile-lipophile balance, and distilling off solvent is at reduced pressure conditions to get Heterocyclic Aramid Fibre modified epoxy resin curing agent.
Step 3 prepares interlaminar bonding material.Above-mentioned Heterocyclic Aramid Fibre modified epoxy is added into epoxy resin
Curing agent, high-speed stirred is uniformly mixed to get a kind of interlaminar bonding material is arrived after ultrasonic disperse processing.
Comparative example 4:
This comparative example provides a kind of interlaminar bonding material, this comparative example difference from Example 2 is, will only prepare
Over-expense polyurethane, the Heterocyclic Aramid Fibre after surface treated and triethylene tetramine be directly appended to prepare ring in epoxy resin
Epoxy resin composite material.
This comparative example based on parts by weight, is made of following raw material: 18 parts of PTMG, 7 parts of IP-DI, succinic anhydride 7
Part, 8 parts of diethanol amine, 5 parts of trimethylolpropane, 35 parts of Heterocyclic Aramid Fibre, 100 parts of epoxy resin, 12 parts of triethylene tetramine.
The selection of raw material and specification are same as Example 1 in this comparative example.
The preparation method of the interlayer materials of this comparative example carries out in accordance with the following steps:
Step 1 carries out preparation and the heterocycle of over-expense polyurethane according to the method for 1 step 1 of embodiment and step 2 respectively
Aramid fiber surface processing.
Step 2 prepares interlaminar bonding material.Into epoxy resin addition over-expense polyurethane and surface treated after it is miscellaneous
Ring aramid fiber after ultrasonic disperse processing, is cut at a high speed uniformly mixed, continues to add triethylene tetramine, high-speed stirring after ultrasonic disperse
It mixes and is uniformly mixed to get a kind of compound interlayer binding material of epoxy resin is arrived.
Comparative example 5:
This comparative example provides a kind of interlaminar bonding material, this comparative example difference from Example 2 is, only that grafting is super
The Heterocyclic Aramid Fibre and triethylene tetramine of branch polyurethane are directly appended to prepare epoxy resin composite material in epoxy resin.
This comparative example based on parts by weight, is made of following raw material: 18 parts of PTMG, 7 parts of IP-DI, succinic anhydride 7
Part, 8 parts of diethanol amine, 5 parts of trimethylolpropane, 35 parts of Heterocyclic Aramid Fibre, 100 parts of epoxy resin, triethylene tetramine 12
Part.
The selection of raw material and specification are same as Example 1 in this comparative example.
The preparation method of the interlayer materials of this comparative example carries out in accordance with the following steps:
Step 1 carries out the over-expense preparation of polyurethane and miscellaneous according to the method for step 1 and step 2 in embodiment 1 respectively
Cyclophane synthetic fibre Fiber strength.
Step 2, the processing of Heterocyclic Aramid Fibre surface grafting.Prepared HBPU is added in reaction kettle, with N, N- diformazan
Base formamide makees diluent, and above-mentioned surface treated Heterocyclic Aramid Fibre is added, be warming up to 80~90 DEG C through ultrasonic wave at
After reason, reaction obtains the heterocycle aramid fiber fibre of surface grafting super branched polyurethane for 5 hours under conditions of high speed shear and catalyst
The modified Heterocyclic Aramid Fibre of super branched polyurethane is separated, purified, dried to obtain in dimension.
Step 3 prepares interlaminar bonding material.The modified heterocycle aramid fiber of above-mentioned super branched polyurethane is added into epoxy resin
Fiber, after ultrasonication, high speed shear is uniformly mixed, and continues to add triethylene tetramine, high-speed stirred after ultrasonic disperse processing
It is uniformly mixed to get a kind of compound interlayer binding material of epoxy resin is arrived.
Comparative example 6:
This comparative example provides a kind of interlaminar bonding material, this comparative example difference from Example 2 is, using etc. quality
Super branched polyurethane substitution Heterocyclic Aramid Fibre epoxy resin is modified, this comparative example based on parts by weight, by following
Raw material are made: 35 parts of PTMG, 14 parts of IP-DI, 14 parts of succinic anhydride, 16 parts of diethanol amine, 10 parts of trimethylolpropane, ring
100 parts of oxygen resin, 12 parts of triethylene tetramine.
The selection of raw material and specification are same as Example 1 in this comparison.
The preparation method of the interlaminar bonding material of this comparative example carries out in accordance with the following steps:
Step 1, according to the preparation method preparation over-expense polyurethane of the aliphatic over-expense polyurethane of embodiment 1.
Step 2, by epoxy resin, triethylene tetramine and super branched polyurethane, high-speed stirred is mixed after ultrasonic disperse processing
It closes and uniformly obtains a kind of interlaminar bonding material.
Comparative example 7:
This comparative example provides a kind of interlaminar bonding material, this comparative example difference from Example 2 is, using etc. quality
Heterocyclic Aramid Fibre substitution over-expense polyurethane epoxy resin is modified.
This comparative example based on parts by weight, is made of following raw material: 75 parts of Heterocyclic Aramid Fibre, 100 parts of epoxy resin,
12 parts of triethylene tetramine.
The selection of raw material and specification are same as Example 1 in this comparative example.
The preparation method of the interlayer materials of this comparative example carries out in accordance with the following steps:
Step 1, Heterocyclic Aramid Fibre surface treatment.After 400 mesh Heterocyclic Aramid Fibres are cleaned by ultrasonic 2h with acetone, it is
Increase the phosphoric acid solution (mass concentration) of addition 20% after fiber surface oxygen-containing functional group content is baked to, impregnates one at 40 DEG C
It is taken out after fixing time, 12h is dried in vacuo at 80 DEG C, reaction certain time in IP-DI solution is added and takes out, it is clear with deionized water
It is washed till neutral and drying, obtains hydroxyl-OH, isocyanate base-NCO and amino-the NH2 fiber for containing high activity in surface.
Step 2, epoxy curing agent preparation.By above-mentioned Heterocyclic Aramid Fibre and epoxy resin bisphenol-A type asphalt mixtures modified by epoxy resin
Rouge E-44, which is dissolved in propylene glycol monomethyl ether and is added in reaction kettle, reacts 3.5h at 70 DEG C with surfactant, adds polyethylene polyamine
Addition reaction is carried out, addition butyl glycidyl ether blocks addition product, is cooled to 50 DEG C of addition ice vinegar after reaction
Acid adjusts hydrophile-lipophile balance, and distilling off solvent is at reduced pressure conditions to get Heterocyclic Aramid Fibre modified epoxy resin curing agent.
Step 3 prepares interlaminar bonding material.Above-mentioned Heterocyclic Aramid Fibre modified epoxy is added into epoxy resin
Curing agent, high-speed stirred is uniformly mixed to get a kind of interlaminar bonding material is arrived after ultrasonic disperse processing.
Comparative example 8:
This comparative example provides a kind of interlaminar bonding material, this comparative example difference from Example 2 is, only with high speed
Shearing, churned mechanically method prepare the modified Heterocyclic Aramid Fibre epoxy curing agent of super branched polyurethane and epoxy resin
Ultrasonication is not used in preparation process for composite material.
This comparative example based on parts by weight, is made of following raw material: 18 parts of PTMG, 7 parts of IP-DI, succinic anhydride 7
Part, 8 parts of diethanol amine, 5 parts of trimethylolpropane, 35 parts of Heterocyclic Aramid Fibre, 100 parts of epoxy resin, triethylene tetramine 15
Part.
The selection of raw material and specification are same as Example 1 in this comparative example.
The preparation method of the interlayer materials of this comparative example carries out in accordance with the following steps:
Step 1 carries out the over-expense preparation of polyurethane and miscellaneous according to the method for step 1 and step 2 in embodiment 1 respectively
Cyclophane synthetic fibre Fiber strength.
Step 2, the processing of Heterocyclic Aramid Fibre surface grafting and epoxy curing agent preparation.Prepared HBPU is added
Enter in reaction kettle, make diluent with n,N-Dimethylformamide, above-mentioned surface treated Heterocyclic Aramid Fibre, heating is added
To 80~90 DEG C, is reacted 5 hours under conditions of high speed shear and catalyst and obtain the heterocycle of surface grafting super branched polyurethane
The modified Heterocyclic Aramid Fibre of super branched polyurethane is separated, purified, dried to obtain in aramid fiber.By the modification heterocycle virtue of above-mentioned preparation
Synthetic fibre fiber and epoxy resin bisphenol A type epoxy resin E-44 are dissolved in propylene glycol monomethyl ether, are added in reaction kettle and exist with surfactant
70 DEG C of reaction 3.5h add polyethylene polyamine and carry out addition reaction, and addition butyl glycidyl ether blocks addition product,
It is cooled to 50 DEG C of addition glacial acetic acid after reaction and adjusts hydrophile-lipophile balance, distilling off solvent is at reduced pressure conditions to get super
Branched polyurethanes are modified Heterocyclic Aramid Fibre epoxy curing agent.
Step 3 prepares interlaminar bonding material.The modified heterocycle aramid fiber of above-mentioned super branched polyurethane is added into epoxy resin
Fibrous epoxy resin curing agent prepares epoxy resin compoiste adhering material, and high-speed stirred is uniformly mixed normal temperature solidified to get arriving
High temperature resistant height glue high-strength high-toughness epoxy resin compounded interlaminar bonding material.
Tensile strength, elongation at break, low temperature flexibility and shearing strength at intersection for verifying interlayer binding material are cut and tension
Intensity is pulled out, according to " Test methods for building waterproof coatings " (GB/T 16777-2008) and " resin-cast body method for testing performance "
The relevant regulations of (GB/T 2567-2008) etc. carry out base to interlaminar bonding material obtained in the embodiment of the present invention and comparative example
This performance test and simulation laboratory test, the results are shown in Table 1.
The performance test results of each embodiment and comparative example of table 1
Comparative example 1~7 is analyzed according to table 1:(A) it is found that overspending polyurethane compared with the epoxy resin of non-modified processing
The toughness and intensity of epoxy resin can be improved respectively with Heterocyclic Aramid Fibre；It is multiple but with the increase of over-expense polyurethane quantity
Condensation material tensile strength is obviously reduced, and elongation at break growth slows down after amount reaches certain value；With Heterocyclic Aramid Fibre number
The increase of amount, fracture of composite materials elongation are obviously reduced, and amount reaches certain value post-tensioning gain in strength and slows down.
(B) comparative example 4 and comparative example 5 are analyzed it is found that with over-expense polyurethane is directlyed adopt and Heterocyclic Aramid Fibre is modified
Epoxy resin is compared, and is used for interlaminar bonding obtained by modified epoxy after overspending the polyurethane grafted surface to Heterocyclic Aramid Fibre
Material has more excellent intensity and toughness；Because it is living that grafting super branched polyurethane can obviously be modified Heterocyclic Aramid Fibre surface
Property, super branched polyurethane surface has a large amount of active groups, can effectively improve its adhesive effect between epoxy resin；And overspend
Changing polyurethane has superior flexibility and resistance to low temperature, improves the flexibility of fiber.
(C) comparative example 5 and embodiment 2 are analyzed it is found that with only by the Heterocyclic Aramid Fibre and three second of grafting over-expense polyurethane
The interlaminar bonding material that alkene tetramine is directly appended to prepare in epoxy resin is compared, and high temperature resistant height glues high-strength and high ductility interlaminar bonding material
Material adhesive property, intensity and toughness are further promoted；Because polyethylene polyamine is grafted on modified Heterocyclic Aramid Fibre,
Make it while being physical crosslinking with epoxy resin and the combination epoxy resin cure of epoxy resin generation chemical bond, fiber
It coheres even closer with resin and stablizes, so that arriving for every excellent properties of over-expense polyurethane and Heterocyclic Aramid Fibre is sufficient
It plays.
(D) Examples 1 to 9 and comparative example 1 are analyzed it is found that compared with the epoxy resin of non-modified processing, system of the present invention
Standby high temperature resistant height glues high-strength and high ductility interlaminar bonding material, and tensile strength and elongation at break significantly improve, and illustrates that material is glutinous
Performance, intensity and toughness is tied to improve；It is bent under the conditions of -20 DEG C, 90 ° and does not crack, illustrate that the anti-low-temperature cracking ability toughness of material increases
By force；Shearing strength declines compared with room temperature (25 DEG C) condition with adhesive strength and is not obvious under the conditions of high temperature (60 DEG C), illustrates material
Expect high temperature resistance enhancing.
(E) analyze embodiment 2 and comparative example 8 it is found that obtained using ultrasonication composite material tensile strength, fracture
Elongation and interlayer shear pull strength are obviously improved compared with composite material prepared by unused ultrasonication, are adopted
It is anti-that the evenly dispersed and contact being unable to reach under mechanical stirring is made it have with ultrasonication nanoscale Heterocyclic Aramid Fibre
Effect is answered, so that over-expense polyurethane and Heterocyclic Aramid Fibre items excellent properties play collaboration enhancing while being not fully exerted
The interlaminar bonding material haveing excellent performance is made in effect.
(F) indices of comparative example 1~9 and comparative example 6~7, it can be found that comprehensive performance indexes is implemented
2 performance of example is most preferably excellent, best raw material composition are as follows: 18 parts of polytetrahydrofuran ether glycol (PTMG, Mn=1000), different Fo Er
7 parts of ketone diisocyanate (IP-DI), 7 parts of succinic anhydride, 8 parts of diethanol amine, 5 parts of trimethylolpropane, epoxy resin 100
Part, 12 parts of triethylene tetramine.
Claims (9)
1. a kind of high temperature resistant height glues high-strength and high ductility interlaminar bonding material, the raw material for preparing the binding material includes epoxy resin,
It is characterized in that, further includes polytetrahydrofuran ether glycol, isophorone diisocyanate, succinic anhydride, diethanol amine, trihydroxy methyl
Propane, Heterocyclic Aramid Fibre and polyethylene polyamine.
2. high temperature resistant height as described in claim 1 glues high-strength and high ductility interlaminar bonding material, which is characterized in that with parts by weight
Meter, is prepared from the following raw materials: 15~20 parts of polytetrahydrofuran ether glycol, 5~10 parts of isophorone diisocyanate, succinic anhydride
5~10 parts, 5~10 parts of diethanol amine, 4~8 parts of trimethylolpropane, 30~40 parts of Heterocyclic Aramid Fibre, epoxy resin 100
Part, 10~15 parts of polyethylene polyamine.
3. high temperature resistant height as described in claim 1 glues high-strength and high ductility interlaminar bonding material, which is characterized in that with parts by weight
Meter, is prepared from the following raw materials: 15~20 parts of polytetrahydrofuran ether glycol, 5~10 parts of isophorone diisocyanate, succinic anhydride
5~8 parts, 5~8 parts of diethanol amine, 4~6 parts of trimethylolpropane, 35 parts of Heterocyclic Aramid Fibre, 100 parts of epoxy resin, more second
12 parts of alkene polyamines.
4. high temperature resistant height as described in claim 1 glues high-strength and high ductility interlaminar bonding material, which is characterized in that with parts by weight
Meter, is prepared from the following raw materials: 18 parts of polytetrahydrofuran ether glycol, 7 parts of isophorone diisocyanate, 7 parts of succinic anhydride, diethyl
8 parts of hydramine, 5 parts of trimethylolpropane, 35 parts of Heterocyclic Aramid Fibre, 100 parts of epoxy resin, 12 parts of polyethylene polyamine.
5. the high temperature resistant height as described in Claims 1-4 any claim glues high-strength and high ductility interlaminar bonding material, feature exists
In the structural formula of the Heterocyclic Aramid Fibre are as follows:
Wherein: n value range is 100~1000.
6. the high temperature resistant height as described in Claims 1-4 any claim glues high-strength and high ductility interlaminar bonding material, feature exists
In the epoxy resin is bisphenol A type epoxy resin E-44.
7. the high temperature resistant height as described in Claims 1-4 any claim glues high-strength and high ductility interlaminar bonding material, feature exists
In the polyethylene polyamine is that any one or more in diethylenetriamine, triethylene tetramine or tetraethylenepentamine is compound.
8. the preparation method that a kind of high temperature resistant height glues high-strength and high ductility interlaminar bonding material, which is characterized in that the preparation method uses
High temperature resistant height described in Claims 1-4 any claim glues the raw material of high-strength and high ductility interlaminar bonding material, and this method includes
Following steps:
Step 1: preparation aliphatic super branched polyurethane:
Using n,N-Dimethylformamide as solvent, the polytetrahydrofuran ether glycol after drying is added, using two fourth of tin dilaurate
Ji Xi is catalyst, and isophorone diisocyanate is added dropwise and reacts 1.5h at 75 DEG C in nitrogen atmosphere, obtains-NCO sealing end
Base polyurethane prepolymer for use as；
With methanol as solvent, succinic anhydride and diethanol amine are added under ice-water bath, reacts 6h in nitrogen atmosphere, it is dry that 4- is (double
(2- ethoxy) imines) -4- ketobutyric acid monomer；Continue trimethylolpropane and above-mentioned 4- (bis- (2- ethoxy) imines)-
4- ketobutyric acid monomer is added in reaction kettle, makees catalyst with toluenesulfonic acid, and toluene is water entrainer, is esterified at 120 DEG C anti-
Answer 8h to anhydrous generation, obtaining faint yellow thick liquid is dissaving polymer；
The dissaving polymer HPAE of preparation, in nitrogen atmosphere, 75 DEG C are added in the above-mentioned base polyurethane prepolymer for use as prepared
Lower reaction 4.5h, obtaining colourless viscous liquid is aliphatic super branched polyurethane；
Step 2: Heterocyclic Aramid Fibre surface treatment:
It is dried after 400 mesh Heterocyclic Aramid Fibres are cleaned by ultrasonic 2h with acetone, then mass concentration is 20%, temperature is 40 DEG C
It is impregnated in phosphoric acid solution, is dried in vacuo 12h at 80 DEG C after immersion, be then added in the solution of isophorone diisocyanate anti-
Answer, spend Ion Cleaning obtained to neutrality and after drying the hydroxyl-OH for containing high activity in surface, isocyanate base-NCO and
The Heterocyclic Aramid Fibre of amino-NH2 surface treatment；
Step 3: the processing of Heterocyclic Aramid Fibre surface grafting:
The aliphatic super branched polyurethane of step 1 preparation is added in reaction kettle, makees diluent with n,N-Dimethylformamide,
The surface treated Heterocyclic Aramid Fibre of above-mentioned steps two is added, at 80~90 DEG C after ultrasonication, in high speed shear
Under conditions of react 5 hours and obtain the Heterocyclic Aramid Fibre of surface grafting super branched polyurethane, be separated, purified, dried to obtain over-expense
Change polyurethane-modified Heterocyclic Aramid Fibre；
Step 4: the preparation of epoxy curing agent:
After the modified Heterocyclic Aramid Fibre of super branched polyurethane obtained in step 3 and epoxy resin are dissolved in propylene glycol monomethyl ether, add
Enter in reaction kettle and react 3.5h at 70 DEG C with surfactant, adds polyethylene polyamine and carry out addition reaction, addition butyl contracting
Water glycerin ether blocks addition product, is cooled to 50 DEG C of addition glacial acetic acid after reaction and adjusts hydrophile-lipophile balance, is subtracting
Distilling off solvent is under the conditions of pressure to get the modified Heterocyclic Aramid Fibre epoxy curing agent of super branched polyurethane；
Step 5: interlaminar bonding material is prepared:
The modified Heterocyclic Aramid Fibre epoxy curing agent of the super branched polyurethane prepared in step 4 is added into epoxy resin,
High-speed stirred is uniformly mixed multiple to get high-strength high-toughness epoxy resin is glued to normal temperature solidified high temperature resistant height after ultrasonic disperse processing
Close interlaminar bonding material.
9. the preparation method that high temperature resistant height as claimed in claim 8 glues high-strength and high ductility interlaminar bonding material, which is characterized in that step
The structural formula for the base polyurethane prepolymer for use as being prepared in rapid one are as follows:
The structural formula for the dissaving polymer being prepared in step 1 are as follows:
The structural formula for the aliphatic super branched polyurethane being prepared in step 1 are as follows:
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698965A (en) * | 2019-11-20 | 2020-01-17 | 广州市白云化工实业有限公司 | Epoxy resin modified polyurethane hyperbranched prepolymer and cement interface agent |
| CN112592689A (en) * | 2021-02-26 | 2021-04-02 | 山东万圣博化工有限公司 | Electronic adhesive and preparation method thereof |
| CN114991730A (en) * | 2022-06-13 | 2022-09-02 | 中海石油(中国)有限公司 | Thick oil thermal recovery simulation interlayer and manufacturing method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150252228A1 (en) * | 2014-03-04 | 2015-09-10 | Frx Polymers, Inc. | Epoxy compositions |
| CN105001427A (en) * | 2015-07-21 | 2015-10-28 | 立邦工业涂料(上海)有限公司 | Amine modified hyper-branched hydroxyl polymer and applications of amine modified hyper-branched hydroxyl polymer in rapid dry and pigment dispersion system |
| CN105803789A (en) * | 2016-03-29 | 2016-07-27 | 深圳市新纶科技股份有限公司 | Surface modification aramid fiber and preparation method thereof |
| CN108276736A (en) * | 2018-01-12 | 2018-07-13 | 大连理工大学 | Oxatyl-containing lateral group hyperbranched polyarylether copolymer cured modified epoxy resin composition, preparation method and application |
| CN108440958A (en) * | 2018-03-12 | 2018-08-24 | 长安大学 | A kind of activeness and quietness high temperature resistant Load materials and preparation method |
-
2018
- 2018-10-19 CN CN201811219012.8A patent/CN109486457B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150252228A1 (en) * | 2014-03-04 | 2015-09-10 | Frx Polymers, Inc. | Epoxy compositions |
| CN105001427A (en) * | 2015-07-21 | 2015-10-28 | 立邦工业涂料(上海)有限公司 | Amine modified hyper-branched hydroxyl polymer and applications of amine modified hyper-branched hydroxyl polymer in rapid dry and pigment dispersion system |
| CN105803789A (en) * | 2016-03-29 | 2016-07-27 | 深圳市新纶科技股份有限公司 | Surface modification aramid fiber and preparation method thereof |
| CN108276736A (en) * | 2018-01-12 | 2018-07-13 | 大连理工大学 | Oxatyl-containing lateral group hyperbranched polyarylether copolymer cured modified epoxy resin composition, preparation method and application |
| CN108440958A (en) * | 2018-03-12 | 2018-08-24 | 长安大学 | A kind of activeness and quietness high temperature resistant Load materials and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| ANDIDEH,M.ET AL.: "Effect of surface modification of electrochemically oxidized carbon fibers by grafting hydroxyl and amine functionalized hyperbranched polyurethanes on interlaminar shear strength of epoxy composites", 《CARBON》 * |
| 强涛涛等: "端羟基超支化聚合物的合成与改性 ", 《日用化学工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698965A (en) * | 2019-11-20 | 2020-01-17 | 广州市白云化工实业有限公司 | Epoxy resin modified polyurethane hyperbranched prepolymer and cement interface agent |
| CN110698965B (en) * | 2019-11-20 | 2021-05-07 | 广州市白云化工实业有限公司 | Epoxy resin modified polyurethane hyperbranched prepolymer and cement interface agent |
| CN112592689A (en) * | 2021-02-26 | 2021-04-02 | 山东万圣博化工有限公司 | Electronic adhesive and preparation method thereof |
| CN114991730A (en) * | 2022-06-13 | 2022-09-02 | 中海石油(中国)有限公司 | Thick oil thermal recovery simulation interlayer and manufacturing method thereof |
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