CN104140782A - Novel epoxy resin adhesive and preparation method thereof - Google Patents
Novel epoxy resin adhesive and preparation method thereof Download PDFInfo
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- CN104140782A CN104140782A CN201410376972.0A CN201410376972A CN104140782A CN 104140782 A CN104140782 A CN 104140782A CN 201410376972 A CN201410376972 A CN 201410376972A CN 104140782 A CN104140782 A CN 104140782A
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Abstract
The invention provides a novel epoxy resin adhesive and a preparation method thereof, relates to an adhesive and a preparation method thereof and aims at solving the problem that an existing epoxy resin adhesive is low in shearing strength and peeling strength, poor in heat resistance and limited in application. The novel epoxy resin adhesive is prepared by, by weight, PU-20 polyurethane modified epoxy resin, epoxy resin E-51, epoxy resin E-44, silane coupling agent and phenolic aldehyde modified amine curing agent. The preparation method comprising the steps of mixing and stirring the PU-20 polyurethane modified epoxy resin, the epoxy resin E-51, the epoxy resin E-44, the silane coupling agent and the phenolic aldehyde modified amine curing agent to obtain liquid adhesive; and then curing the liquid adhesive to obtain the novel epoxy resin adhesive. The novel epoxy resin adhesive can be obtained by means of the preparation method.
Description
Technical field
The present invention relates to a kind of sizing agent and preparation method thereof.
Background technology
Epoxy adhesive is widely used because of its excellent cementability, wear resistance, mechanical property, electrical insulation capability, chemical stability, weather resistance, again because its cured article fragility is larger, the shortcoming that toughness is not good, has limited it in the application of some precision, leading-edge field.And ether amine is a class intrinsic toughening type solidifying agent, its feature is water white transparency, low viscosity, boiling point is high, steam forces down, toxicity is little, medium activity, curing exotherm temperature are low, good with epoxy resin compatibility, cured article water white transparency, high gloss, good toughness, heat shock resistance, low-temperature performance are good etc.But its cured article is not very desirable aspect resistance to elevated temperatures, and aliphatic cyclic amine is a kind of solidifying agent of excellent heat resistance.Phenol aldehyde modified amine can have been introduced phenolic hydroxyl group and amine active hydrogen in the molecule of modifier, greatly strengthened reactive behavior, improved the curing speed of amido and epoxide group, simultaneously with phenolic aldehyde skeleton structure also can further improve heat-drawn wire, improve thermotolerance and the erosion resistance of resin cured matter itself.
The people such as the J.J.LIN in Taiwan have studied the building-up reactions mechanism of ether amine, formaldehyde, phenol etc., the performance of modification ether amine BAEE, EDR-148, EDR-192 and E-51 epoxy resin cured product is studied simultaneously, bonding strength at its 25 ℃ is 28.27MPa, and the T stripping strength at 25 ℃ is 0.75kNm
-1.The external people such as Speranza first synthesize two alkylphenol intermediates with formaldehyde and ether amine with nonyl phenol, and then this intermediate further reacts and obtains product with formaldehyde and another kind of ether amine again, and intermediate and product all can be made the solidifying agent of epoxy resin.
Summary of the invention
The shearing resistance and the stripping strength that the object of the invention is to solve existing epoxy resin adhesive are all low, poor heat resistance, and the problem that application is restricted, and a kind of Novel epoxy reins adhesive and preparation method thereof is provided.
A kind of Novel epoxy reins adhesive is prepared from by 120 parts～130 parts PU-20 polyurethane modified epoxy resins, 0 part～100 parts epoxy resin E-51,0 part～100 parts epoxy resin E-44s, 0.5 part～2 parts silane coupling agents and 40～100 parts of phenol aldehyde modified amine hardeners by weight.
A kind of preparation method of Novel epoxy reins adhesive specifically completes according to the following steps: under the condition that is 60r/min～120r/min in room temperature and stirring velocity, mark mixes 120 parts～130 parts PU-20 polyurethane modified epoxy resins, 0 part～100 parts epoxy resin E-51,0 part～100 parts epoxy resin E-44s, 0.5 part～2 parts silane coupling agents and 40 parts～100 parts phenol aldehyde modified amine hardeners by weight, stir 10min～12min, obtain liquid sizing agent; Again liquid sizing agent is at 25 ℃, to solidify 7d～10d or is at 80 ℃, to solidify 3h～4h in temperature in temperature, obtain Novel epoxy reins adhesive;
The preparation method of described phenol aldehyde modified amine hardener completes according to the following steps:
1., first in reactor, add methyl cyclohexane diamines and phenol, low whipping speed is that under the condition of 200r/min～500r/min, the temperature rise rate with 2 ℃/min～5 ℃/min is warming up to 80 ℃～85 ℃ from room temperature, the rate of addition of 60/min～100 droplet/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h～3h at 80 ℃～85 ℃ in temperature, obtain intermediate reaction product;
2., in intermediate reaction product, add ether amine again, the rate of addition of 60/min～100 droplet/min of take again adds the formalin that massfraction is 37%, then from temperature, be 80 ℃～85 ℃ and be warming up to 100 ℃～105 ℃, and be back flow reaction 3h～4h at 100 ℃～105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener;
The methyl cyclohexane diamines of step described in 1. with the molar mass of phenol than being (0.9～1.1): 1;
The methyl cyclohexane diamines of step described in 1. with the molar mass of formaldehyde than being (0.9～1.1): 1;
Step 2. described ether amine is one or more the mixture in EDR-104, EDR-176, D-230, T-403, XTJ-435 and XTJ-436;
Step 1. the molar mass of described methyl cyclohexane diamines and the step ether amine described in 2. than being 1:(1.9～2.1);
The mass ratio of the formalin that the formalin that the massfraction of step described in is 1. 37% and the step massfraction described in is 2. 37% is 1:2.
Ether amine EDR-104 of the present invention, EDR-176, D-230, T-403, XTJ-435 and XTJ-436 produce by U.S. HUNTSMAN company;
PU-20 polyurethane modified epoxy resin Shi You Institute of Petrochemistry, HLJ Academy of Science described in the present invention produces, PU/EP=20/100;
The structure of the methyl cyclohexane diamines described in the present invention is:
The structural formula of ether amine EDR-104 described in the present invention is:
The structural formula of EDR-176 described in the present invention is
The structural formula of D-230 described in the present invention is
The structural formula of T-403 described in the present invention is
x+y+z=5～6 wherein;
The structural formula of XTJ-435 described in the present invention is
The structural formula of XTJ-436 described in the present invention is
In the present invention intermediate reaction product mainly by
form.
Advantage of the present invention:
The present invention improves the adhesiveproperties of tackiness agent by introduce phenolic aldehyde skeleton and aliphatic cyclic amine in polyetheramine solidifying agent; The present invention combines methyl cyclohexane diamines and ether amine, phenol and formaldehyde by organic reaction, make the autocatalysis type solidifying agent with phenolic hydroxyl group, has both had hard section of good heat resistance in its molecule, has again good soft section of snappiness; By itself and polyurethane modified epoxy resin, epoxy resin, silane coupling agent blend, make neo-epoxy resin tackiness agent again, the second-order transition temperature of Novel epoxy reins adhesive prepared by the present invention is 85.02 ℃～93.03 ℃; 25 ℃ of down cut intensity reach 35.21MPa～42.01MPa, and 80 ℃ of down cut intensity reach 16.73MPa～25.96MPa, and 90 ° of stripping strengths reach 6.38kNm at 25 ℃
-1～7.82kNm
-1, can make sqtructural adhesive and use.
The present invention can obtain a kind of Novel epoxy reins adhesive.
Embodiment
Embodiment one: present embodiment is that a kind of Novel epoxy reins adhesive is prepared from by 120 parts～130 parts PU-20 polyurethane modified epoxy resins, 0 part～100 parts epoxy resin E-51,0 part～100 parts epoxy resin E-44s, 0.5 part～2 parts silane coupling agents and 40～100 parts of phenol aldehyde modified amine hardeners by weight.
PU-20 polyurethane modified epoxy resin Shi You Institute of Petrochemistry, HLJ Academy of Science described in this embodiment produces, PU/EP=20/100;
The advantage of this embodiment:
This embodiment improves the adhesiveproperties of tackiness agent by introduce phenolic aldehyde skeleton and aliphatic cyclic amine in polyetheramine solidifying agent; This embodiment combines methyl cyclohexane diamines and ether amine, phenol and formaldehyde by organic reaction, make the autocatalysis type solidifying agent with phenolic hydroxyl group, has both had hard section of good heat resistance in its molecule, has again good soft section of snappiness; By itself and polyurethane modified epoxy resin, epoxy resin, silane coupling agent blend, make neo-epoxy resin tackiness agent again, the second-order transition temperature of Novel epoxy reins adhesive prepared by this embodiment is 85.02 ℃～93.03 ℃; 25 ℃ of down cut intensity reach 35.21MPa～42.01MPa, and 80 ℃ of down cut intensity reach 16.73MPa～25.96MPa, and 90 ° of stripping strengths reach 6.38kNm at 25 ℃
-1～7.82kNm
-1, can make sqtructural adhesive and use.
This embodiment can obtain a kind of Novel epoxy reins adhesive.
Embodiment two: present embodiment and embodiment one difference are: described silane coupling agent is KH560, KH580 or KH590.Other steps are identical with embodiment one.
Embodiment three: present embodiment and one of embodiment one or two difference are: the preparation method of described phenol aldehyde modified amine hardener, completes according to the following steps:
1., first in reactor, add methyl cyclohexane diamines and phenol, low whipping speed is that under the condition of 200r/min～500r/min, the temperature rise rate with 2 ℃/min～5 ℃/min is warming up to 80 ℃～85 ℃ from room temperature, the rate of addition of 60/min～100 droplet/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h～3h at 80 ℃～85 ℃ in temperature, obtain intermediate reaction product;
2., in intermediate reaction product, add ether amine again, the rate of addition of 60/min～100 droplet/min of take again adds the formalin that massfraction is 37%, then from temperature, be 80 ℃～85 ℃ and be warming up to 100 ℃～105 ℃, and be back flow reaction 3h～4h at 100 ℃～105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener;
The methyl cyclohexane diamines of step described in 1. with the molar mass of phenol than being (0.9～1.1): 1;
The methyl cyclohexane diamines of step described in 1. with the molar mass of formaldehyde than being (0.9～1.1): 1;
Step 1. the molar mass of described methyl cyclohexane diamines and the step ether amine described in 2. than being 1:(1.9～2.1);
The mass ratio of the formalin that the formalin that the massfraction of step described in is 1. 37% and the step massfraction described in is 2. 37% is 1:2.Other steps are identical with embodiment one or two.
The structure of the methyl cyclohexane diamines described in this embodiment is:
In this embodiment intermediate reaction product mainly by
form.
Embodiment four: one of present embodiment and embodiment one to three difference is: first step adds methyl cyclohexane diamines and phenol in 1. in reactor, low whipping speed is that under the condition of 300r/min, the temperature rise rate with 4 ℃/min is warming up to 85 ℃ from room temperature, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h at 85 ℃ in temperature, obtain intermediate reaction product.
Other steps are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: step adds ether amine in 2. again in intermediate reaction product, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, then from temperature, be 85 ℃ and be warming up to 105 ℃, and be back flow reaction 3h at 105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener.Other steps are identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five difference is: step 2. described ether amine is one or more the mixture in EDR-104, EDR-176, D-230, T-403, XTJ-435 and XTJ-436.Other steps are identical with embodiment one to five.
When ether amine is mixture, the ratio between each material be arbitrarily than.
Ether amine EDR-104, EDR-176, D-230, T-403, XTJ-435 and XTJ-436 described in this embodiment produces by U.S. HUNTSMAN company;
The structural formula of ether amine EDR-104 described in this embodiment is:
The structural formula of EDR-176 described in this embodiment is
The structural formula of D-230 described in this embodiment is
The structural formula of T-403 described in this embodiment is
x+y+z=5～6 wherein;
The structural formula of XTJ-435 described in this embodiment is
The structural formula of XTJ-436 described in this embodiment is
Embodiment seven: present embodiment is a kind of preparation method of Novel epoxy reins adhesive, specifically complete according to the following steps: under the condition that is 60r/min～120r/min in room temperature and stirring velocity, mark mixes 120 parts～130 parts PU-20 polyurethane modified epoxy resins, 0 part～100 parts epoxy resin E-51,0 part～100 parts epoxy resin E-44s, 0.5 part～2 parts silane coupling agents and 40 parts～100 parts phenol aldehyde modified amine hardeners by weight, stir 10min～12min, obtain liquid sizing agent; Again liquid sizing agent is at 25 ℃, to solidify 7d～10d or is at 80 ℃, to solidify 3h～4h in temperature in temperature, obtain Novel epoxy reins adhesive;
The preparation method of described phenol aldehyde modified amine hardener completes according to the following steps:
1., first in reactor, add methyl cyclohexane diamines and phenol, low whipping speed is that under the condition of 200r/min～500r/min, the temperature rise rate with 2 ℃/min～5 ℃/min is warming up to 80 ℃～85 ℃ from room temperature, the rate of addition of 60/min～100 droplet/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h～3h at 80 ℃～85 ℃ in temperature, obtain intermediate reaction product;
2., in intermediate reaction product, add ether amine again, the rate of addition of 60/min～100 droplet/min of take again adds the formalin that massfraction is 37%, then from temperature, be 80 ℃～85 ℃ and be warming up to 100 ℃～105 ℃, and be back flow reaction 3h～4h at 100 ℃～105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener;
The methyl cyclohexane diamines of step described in 1. with the molar mass of phenol than being (0.9～1.1): 1;
The methyl cyclohexane diamines of step described in 1. with the molar mass of formaldehyde than being (0.9～1.1): 1;
Step 2. described ether amine is one or more the mixture in EDR-104, EDR-176, D-230, T-403, XTJ-435 and XTJ-436;
Step 1. the molar mass of described methyl cyclohexane diamines and the step ether amine described in 2. than being 1:(1.9～2.1);
The mass ratio of the formalin that the formalin that the massfraction of step described in is 1. 37% and the step massfraction described in is 2. 37% is 1:2.
In this embodiment intermediate reaction product mainly by
form.
The advantage of this embodiment:
This embodiment improves the adhesiveproperties of tackiness agent by introduce phenolic aldehyde skeleton and aliphatic cyclic amine in polyetheramine solidifying agent; This embodiment combines methyl cyclohexane diamines and ether amine, phenol and formaldehyde by organic reaction, make the autocatalysis type solidifying agent with phenolic hydroxyl group, has both had hard section of good heat resistance in its molecule, has again good soft section of snappiness; By itself and polyurethane modified epoxy resin, epoxy resin, silane coupling agent blend, make neo-epoxy resin tackiness agent again, the second-order transition temperature of Novel epoxy reins adhesive prepared by this embodiment is 85.02 ℃～93.03 ℃; 25 ℃ of down cut intensity reach 35.21MPa～42.01MPa, and 80 ℃ of down cut intensity reach 16.73MPa～25.96MPa, and 90 ° of stripping strengths reach 6.38kNm at 25 ℃
-1～7.82kNm
-1, can make sqtructural adhesive and use.
This embodiment can obtain a kind of Novel epoxy reins adhesive.
Embodiment eight: present embodiment and embodiment seven differences are: described silane coupling agent is KH560, KH580 or KH590.Other steps are identical with embodiment seven.
Embodiment nine: present embodiment and one of embodiment seven or eight difference are: under the condition that is 60r/min～120r/min in room temperature and stirring velocity, mark mixes 120 parts～130 parts PU-20 polyurethane modified epoxy resins, 0.5 part～2 parts silane coupling agents and 40 parts～100 parts phenol aldehyde modified amine hardeners by weight, stir 10min～12min, obtain liquid sizing agent; Again liquid sizing agent is at 25 ℃, to solidify 7d～10d or is at 80 ℃, to solidify 3h～4h in temperature in temperature, obtain Novel epoxy reins adhesive.Other steps are identical with embodiment seven or eight.
Embodiment ten: one of present embodiment and embodiment seven to nine difference is: under the condition that is 60r/min～120r/min in room temperature and stirring velocity, mark mixes 120 parts of PU-20 polyurethane modified epoxy resins, 20 parts of epoxy resin E-51,30 parts of E-44,1 part of silane coupling agent and 80 parts of phenol aldehyde modified amine hardeners by weight, stir 10min～12min, obtain liquid sizing agent; Again liquid sizing agent is at 25 ℃, to solidify 7d～10d or is at 80 ℃, to solidify 3h～4h in temperature in temperature, obtain Novel epoxy reins adhesive.Other steps are identical with embodiment seven to nine.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: a kind of preparation method of Novel epoxy reins adhesive, specifically complete according to the following steps: under the condition that is 90r/min in room temperature and stirring velocity, mark mixes the phenol aldehyde modified amine hardener of 120g PU-20 polyurethane modified epoxy resin, 1g silane coupling agent and 40g by weight, stir 10min, obtain liquid sizing agent; By liquid sizing agent, in temperature, be at 80 ℃, to solidify 3h again, obtain Novel epoxy reins adhesive;
Described silane coupling agent is KH580;
The preparation method of described phenol aldehyde modified amine hardener, completes according to the following steps:
1., first in reactor, add 64.1g methyl cyclohexane diamines and phenol, low whipping speed is that under the condition of 350r/min, the temperature rise rate with 3.5 ℃/min is warming up to 85 ℃ from room temperature, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h at 85 ℃ in temperature, obtain intermediate reaction product;
2., in intermediate reaction product, add ether amine again, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, then from temperature, be 85 ℃ and be warming up to 105 ℃, and be back flow reaction 3h at 105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener;
The methyl cyclohexane diamines of step described in 1. with the molar mass of phenol than being 1:1;
The methyl cyclohexane diamines of step described in 1. with the molar mass of formaldehyde than being 1.1:1;
Step 2. described ether amine is EDR-104; The structural formula of described ether amine EDR-104 is:
described ether amine EDR-104 is produced by U.S. HUNTSMAN company;
Step 1. the molar mass of described methyl cyclohexane diamines and the step ether amine described in 2. than being 1:2;
The mass ratio of the formalin that the formalin that the massfraction of step described in is 1. 37% and the step massfraction described in is 2. 37% is 1:2.
The second-order transition temperature of the Novel epoxy reins adhesive of test one preparation is 93.03 ℃; 25 ℃ of down cut intensity, be 36.78MPa, 80 ℃ of down cut intensity are 25.96MPa, and 90 ° of stripping strengths are 6.38kNm at 25 ℃
-1.
Test two: a kind of preparation method of Novel epoxy reins adhesive, specifically complete according to the following steps: under the condition that is 90r/min in room temperature and stirring velocity, mark mixes the phenol aldehyde modified amine hardener of 120g PU-20 polyurethane modified epoxy resin, 1g silane coupling agent and 40g by weight, stir 10min, obtain liquid sizing agent; By liquid sizing agent, in temperature, be at 25 ℃, to solidify 7d again, obtain Novel epoxy reins adhesive;
Described silane coupling agent is KH580;
The preparation method of described phenol aldehyde modified amine hardener, completes according to the following steps:
1., first in reactor, add 64.1g methyl cyclohexane diamines and phenol, low whipping speed is that under the condition of 350r/min, the temperature rise rate with 3.5 ℃/min is warming up to 85 ℃ from room temperature, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h at 85 ℃ in temperature, obtain intermediate reaction product;
2., in intermediate reaction product, add ether amine again, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, then from temperature, be 85 ℃ and be warming up to 105 ℃, and be back flow reaction 3h at 105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener;
The methyl cyclohexane diamines of step described in 1. with the molar mass of phenol than being 0.9:1;
The methyl cyclohexane diamines of step described in 1. with the molar mass of formaldehyde than being 1:1;
Step 2. described ether amine is EDR-104; The structural formula of described ether amine EDR-104 is:
described ether amine EDR-104 is produced by U.S. HUNTSMAN company;
Step 1. the molar mass of described methyl cyclohexane diamines and the step ether amine described in 2. than being 1:2.1;
The mass ratio of the formalin that the formalin that the massfraction of step described in is 1. 37% and the step massfraction described in is 2. 37% is 1:2.
The second-order transition temperature of the Novel epoxy reins adhesive of test two preparations is 90.35 ℃; At 25 ℃ of down cut intensity 35.21MPa, 80 ℃ of down cut intensity 23.39MPa, 90 ° of stripping strength 6.74kNm at 25 ℃
-1.
Test three: a kind of preparation method of Novel epoxy reins adhesive, specifically completes according to the following steps:
Under the condition that is 90r/min in room temperature and stirring velocity, mark mixes the phenol aldehyde modified amine hardener of 120g PU-20 polyurethane modified epoxy resin, 50g epoxy resin E-44,1g silane coupling agent and 100g by weight, stirs 10min, obtains liquid sizing agent; By liquid sizing agent, in temperature, be at 80 ℃, to solidify 3h again, obtain Novel epoxy reins adhesive;
Described silane coupling agent is KH590;
The preparation method of described phenol aldehyde modified amine hardener, completes according to the following steps:
1., first in reactor, add 64.1g methyl cyclohexane diamines and phenol, low whipping speed is that under the condition of 350r/min, the temperature rise rate with 3.5 ℃/min is warming up to 85 ℃ from room temperature, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h at 85 ℃ in temperature, obtain intermediate reaction product;
2., in intermediate reaction product, add ether amine again, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, then from temperature, be 85 ℃ and be warming up to 105 ℃, and be back flow reaction 3h at 105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener;
The methyl cyclohexane diamines of step described in 1. with the molar mass of phenol than being 1:1;
The methyl cyclohexane diamines of step described in 1. with the molar mass of formaldehyde than being 1:1;
Step 2. described ether amine is the mixture of EDR-176 and XTJ-436; In described ether amine, EDR-176 is 0.9:0.1 with the molar mass ratio of XTJ-436;
The structural formula of described EDR-176 is
the structural formula of described XTJ-436 is
described EDR-176 and XTJ-436 are produced by U.S. HUNTSMAN company;
Step 1. the molar mass of described methyl cyclohexane diamines and the step ether amine described in 2. than being 1:2;
The mass ratio of the formalin that the formalin that the massfraction of step described in is 1. 37% and the step massfraction described in is 2. 37% is 1:2.
The second-order transition temperature of the Novel epoxy reins adhesive of test three preparations is 89.61 ℃; 25 ℃ of down cut intensity, be 36.79MPa, 80 ℃ of down cut intensity are 23.86MPa, and 90 ° of stripping strengths are 7.64kNm at 25 ℃
-1.
Test four: a kind of preparation method of Novel epoxy reins adhesive, specifically completes according to the following steps:
Under the condition that is 90r/min in room temperature and stirring velocity, mark mixes the phenol aldehyde modified amine hardener of 120g PU-20 polyurethane modified epoxy resin, 50g epoxy resin E-44,1g silane coupling agent and 100g by weight, stirs 10min, obtains liquid sizing agent; By liquid sizing agent, in temperature, be at 25 ℃, to solidify 7d again, obtain Novel epoxy reins adhesive;
Described silane coupling agent is KH590;
The preparation method of described phenol aldehyde modified amine hardener, completes according to the following steps:
1., first in reactor, add 64.1g methyl cyclohexane diamines and phenol, low whipping speed is that under the condition of 350r/min, the temperature rise rate with 3.5 ℃/min is warming up to 85 ℃ from room temperature, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h at 85 ℃ in temperature, obtain intermediate reaction product;
2., in intermediate reaction product, add ether amine again, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, then from temperature, be 85 ℃ and be warming up to 105 ℃, and be back flow reaction 3h at 105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener;
The methyl cyclohexane diamines of step described in 1. with the molar mass of phenol than being 1:1;
The methyl cyclohexane diamines of step described in 1. with the molar mass of formaldehyde than being 0.9:1;
Step 2. described ether amine is the mixture of EDR-176 and XTJ-436; In described ether amine, EDR-176 is 0.9:0.1 with the molar mass ratio of XTJ-436;
The structural formula of described EDR-176 is
the structural formula of described XTJ-436 is
described EDR-176 and XTJ-436 are produced by U.S. HUNTSMAN company;
Step 1. the molar mass of described methyl cyclohexane diamines and the step ether amine described in 2. than being 1:1.9;
The mass ratio of the formalin that the formalin that the massfraction of step described in is 1. 37% and the step massfraction described in is 2. 37% is 1:2.
The second-order transition temperature of the Novel epoxy reins adhesive of test four preparations is 88.13 ℃; 25 ℃ of down cut intensity, be 39.62MPa, 80 ℃ of down cut intensity are 20.66MPa, and 90 ° of stripping strengths are 7.62kNm at 25 ℃
-1.
Test five: a kind of preparation method of Novel epoxy reins adhesive specifically completes according to the following steps:
Under the condition that is 90r/min in room temperature and stirring velocity, mark mixes the phenol aldehyde modified amine hardener of 120g PU-20 polyurethane modified epoxy resin, 20g epoxy resin E-51,30g epoxy resin E-44,1g silane coupling agent and 80g by weight, stir 10min, obtain liquid sizing agent; By liquid sizing agent, in temperature, be at 80 ℃, to solidify 3h again, obtain Novel epoxy reins adhesive;
Described silane coupling agent is KH560;
The preparation method of described phenol aldehyde modified amine hardener, completes according to the following steps:
1., first in reactor, add 64.1g methyl cyclohexane diamines and phenol, low whipping speed is that under the condition of 350r/min, the temperature rise rate with 3.5 ℃/min is warming up to 85 ℃ from room temperature, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h at 85 ℃ in temperature, obtain intermediate reaction product;
2., in intermediate reaction product, add ether amine again, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, then from temperature, be 85 ℃ and be warming up to 105 ℃, and be back flow reaction 3h at 105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener;
The methyl cyclohexane diamines of step described in 1. with the molar mass of phenol than being 0.9:1;
The methyl cyclohexane diamines of step described in 1. with the molar mass of formaldehyde than being 1:1;
Step 2. described ether amine is the mixture of T-403 and XTJ-435; In described ether amine, T-403 is 0.9:0.1 with the molar mass ratio of XTJ-435;
The structural formula of described T-403 is
the structural formula of described XTJ-435 is
described T-403 and XTJ-435 are produced by U.S. HUNTSMAN company;
Step 1. the molar mass of described methyl cyclohexane diamines and the step ether amine described in 2. than being 1:2;
The mass ratio of the formalin that the formalin that the massfraction of step described in is 1. 37% and the step massfraction described in is 2. 37% is 1:2.
The second-order transition temperature of the Novel epoxy reins adhesive of test five preparations is 86.47 ℃; 25 ℃ of down cut intensity, be 42.01MPa, 80 ℃ of down cut intensity are 18.92MPa, and 90 ° of stripping strengths are 7.69kNm at 25 ℃
-1.
Test six: a kind of preparation method of Novel epoxy reins adhesive specifically completes according to the following steps:
Under the condition that is 90r/min in room temperature and stirring velocity, mark mixes the phenol aldehyde modified amine hardener of 120g PU-20 polyurethane modified epoxy resin, 20g epoxy resin E-51,30g epoxy resin E-44,1g silane coupling agent and 80g by weight, stir 10min, obtain liquid sizing agent; By liquid sizing agent, in temperature, be at 25 ℃, to solidify 7d again, obtain Novel epoxy reins adhesive;
Described silane coupling agent is KH560;
The preparation method of described phenol aldehyde modified amine hardener, completes according to the following steps:
1., first in reactor, add 64.1g methyl cyclohexane diamines and phenol, low whipping speed is that under the condition of 350r/min, the temperature rise rate with 3.5 ℃/min is warming up to 85 ℃ from room temperature, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h at 85 ℃ in temperature, obtain intermediate reaction product;
2., in intermediate reaction product, add ether amine again, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, then from temperature, be 85 ℃ and be warming up to 105 ℃, and be back flow reaction 3h at 105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener;
The methyl cyclohexane diamines of step described in 1. with the molar mass of phenol than being 1:1;
The methyl cyclohexane diamines of step described in 1. with the molar mass of formaldehyde than being 1:1;
Step 2. described ether amine is the mixture of T-403 and XTJ-435; In described ether amine, T-403 is 0.9:0.1 with the molar mass ratio of XTJ-435;
The structural formula of described T-403 is
the structural formula of described XTJ-435 is
described T-403 and XTJ-435 are produced by U.S. HUNTSMAN company;
Step 1. the molar mass of described methyl cyclohexane diamines and the step ether amine described in 2. than being 1:2;
The mass ratio of the formalin that the formalin that the massfraction of step described in is 1. 37% and the step massfraction described in is 2. 37% is 1:2.
The second-order transition temperature of the Novel epoxy reins adhesive of test six preparations is 85.02 ℃; 25 ℃ of down cut intensity, be 40.61MPa, 80 ℃ of down cut intensity are 16.73MPa, and 90 ° of stripping strengths are 7.82kNm at 25 ℃
-1.
Test seven: a kind of preparation method of Novel epoxy reins adhesive specifically completes according to the following steps:
Under the condition that is 90r/min in room temperature and stirring velocity, mark mixes the phenol aldehyde modified amine hardener of 130g PU-20 polyurethane modified epoxy resin, 60g epoxy resin E-51,1g silane coupling agent and 80g by weight, stirs 10min, obtains liquid sizing agent; By liquid sizing agent, in temperature, be at 80 ℃, to solidify 3h again, obtain Novel epoxy reins adhesive;
Described silane coupling agent is KH-560;
The preparation method of described phenol aldehyde modified amine hardener, completes according to the following steps:
1., first in reactor, add 64.1g methyl cyclohexane diamines and phenol, low whipping speed is that under the condition of 350r/min, the temperature rise rate with 3.5 ℃/min is warming up to 85 ℃ from room temperature, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h at 85 ℃ in temperature, obtain intermediate reaction product;
2., in intermediate reaction product, add ether amine again, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, then from temperature, be 85 ℃ and be warming up to 105 ℃, and be back flow reaction 3h at 105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener;
The methyl cyclohexane diamines of step described in 1. with the molar mass of phenol than being 1:1;
The methyl cyclohexane diamines of step described in 1. with the molar mass of formaldehyde than being 1:1;
Step 2. described ether amine is the mixture of D-230 and T-403; In described ether amine, D-230 is 1:1 with the molar mass ratio of T-403;
The structural formula of described D-230 is
the structural formula of described T-403
described D-230 and T-403 are produced by U.S. HUNTSMAN company;
Step 1. the molar mass of described methyl cyclohexane diamines and the step ether amine described in 2. than being 1:2.1;
The mass ratio of the formalin that the formalin that the massfraction of step described in is 1. 37% and the step massfraction described in is 2. 37% is 1:2.
The second-order transition temperature of the Novel epoxy reins adhesive of test seven preparations is 87.27 ℃; 25 ℃ of down cut intensity, be 39.05MPa, 80 ℃ of down cut intensity are 22.46MPa, and 90 ° of stripping strengths are 6.54kNm at 25 ℃
-1.
Test eight: a kind of preparation method of Novel epoxy reins adhesive specifically completes according to the following steps:
Under the condition that is 90r/min in room temperature and stirring velocity, mark mixes the phenol aldehyde modified amine hardener of 120g PU-20 polyurethane modified epoxy resin, 60g epoxy resin E-51,1g silane coupling agent and 80g by weight, stirs 10min, obtains liquid sizing agent; By liquid sizing agent, in temperature, be at 25 ℃, to solidify 7d again, obtain Novel epoxy reins adhesive;
Described silane coupling agent is KH-560;
The preparation method of described phenol aldehyde modified amine hardener, completes according to the following steps:
1., first in reactor, add 64.1g methyl cyclohexane diamines and phenol, low whipping speed is that under the condition of 350r/min, the temperature rise rate with 3.5 ℃/min is warming up to 85 ℃ from room temperature, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h at 85 ℃ in temperature, obtain intermediate reaction product;
2., in intermediate reaction product, add ether amine again, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, then from temperature, be 85 ℃ and be warming up to 105 ℃, and be back flow reaction 3h at 105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener;
The methyl cyclohexane diamines of step described in 1. with the molar mass of phenol than being 1.1:1;
The methyl cyclohexane diamines of step described in 1. with the molar mass of formaldehyde than being 1.1:1;
Step 2. described ether amine is the mixture of D-230, XTJ-435 and T-403; In described ether amine, be that D-230 is 0.9:0.1 with the molar mass ratio of XTJ-435; D-230 is 1:2 with the molar mass ratio of T-403;
The structural formula of described D-230 is
the structural formula of described XTJ-435 is
the structural formula of described T-403
described D-230, XTJ-435 and T-403 are produced by U.S. HUNTSMAN company;
Step 1. the molar mass of described methyl cyclohexane diamines and the step ether amine described in 2. than being 1:2;
The mass ratio of the formalin that the formalin that the massfraction of step described in is 1. 37% and the step massfraction described in is 2. 37% is 1:2.
The second-order transition temperature of the Novel epoxy reins adhesive of test eight preparations is 86.33 ℃; 25 ℃ of down cut intensity, be 41.04MPa, 80 ℃ of down cut intensity are 20.15MPa, and 90 ° of stripping strengths are 7.03kNm at 25 ℃
-1.
Claims (10)
1. a Novel epoxy reins adhesive, is characterized in that a kind of Novel epoxy reins adhesive is prepared from by 120 parts～130 parts PU-20 polyurethane modified epoxy resins, 0 part～100 parts epoxy resin E-51,0 part～100 parts epoxy resin E-44s, 0.5 part～2 parts silane coupling agents and 40～100 parts of phenol aldehyde modified amine hardeners by weight.
2. a kind of Novel epoxy reins adhesive according to claim 1, is characterized in that described silane coupling agent is KH560, KH580 or KH590.
3. a kind of Novel epoxy reins adhesive according to claim 1, is characterized in that the preparation method of described phenol aldehyde modified amine hardener completes according to the following steps:
1., first in reactor, add methyl cyclohexane diamines and phenol, low whipping speed is that under the condition of 200r/min～500r/min, the temperature rise rate with 2 ℃/min～5 ℃/min is warming up to 80 ℃～85 ℃ from room temperature, the rate of addition of 60/min～100 droplet/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h～3h at 80 ℃～85 ℃ in temperature, obtain intermediate reaction product;
2., in intermediate reaction product, add ether amine again, the rate of addition of 60/min～100 droplet/min of take again adds the formalin that massfraction is 37%, then from temperature, be 80 ℃～85 ℃ and be warming up to 100 ℃～105 ℃, and be back flow reaction 3h～4h at 100 ℃～105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener;
The methyl cyclohexane diamines of step described in 1. with the molar mass of phenol than being (0.9～1.1): 1;
The methyl cyclohexane diamines of step described in 1. with the molar mass of formaldehyde than being (0.9～1.1): 1;
Step 1. the molar mass of described methyl cyclohexane diamines and the step ether amine described in 2. than being 1:(1.9～2.1);
The mass ratio of the formalin that the formalin that the massfraction of step described in is 1. 37% and the step massfraction described in is 2. 37% is 1:2.
4. a kind of Novel epoxy reins adhesive according to claim 3, it is characterized in that first in reactor, adding methyl cyclohexane diamines and phenol during step 1., low whipping speed is that under the condition of 300r/min, the temperature rise rate with 4 ℃/min is warming up to 85 ℃ from room temperature, the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h at 85 ℃ in temperature, obtain intermediate reaction product.
5. a kind of Novel epoxy reins adhesive according to claim 3, it is characterized in that in intermediate reaction product, adding ether amine again during step 2., the rate of addition of 80/min of take again adds the formalin that massfraction is 37%, then from temperature, be 85 ℃ and be warming up to 105 ℃, and be back flow reaction 3h at 105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener.
6. a kind of Novel epoxy reins adhesive according to claim 3, it is characterized in that step 2. described ether amine be one or more the mixture in EDR-104, EDR-176, D-230, T-403, XTJ-435 and XTJ-436.
7. the preparation method of a kind of Novel epoxy reins adhesive as claimed in claim 1, it is characterized in that a kind of preparation method of Novel epoxy reins adhesive specifically completes according to the following steps: under the condition that is 60r/min～120r/min in room temperature and stirring velocity, mark is by 120 parts～130 parts PU-20 polyurethane modified epoxy resins by weight, 0 part～100 parts epoxy resin E-51, 0 part～100 parts epoxy resin E-44s, 0.5 part～2 parts silane coupling agents and 40 parts～100 parts phenol aldehyde modified amine hardeners mix, stir 10min～12min, obtain liquid sizing agent, again liquid sizing agent is at 25 ℃, to solidify 7d～10d or is at 80 ℃, to solidify 3h～4h in temperature in temperature, obtain Novel epoxy reins adhesive,
The preparation method of described phenol aldehyde modified amine hardener completes according to the following steps:
1., first in reactor, add methyl cyclohexane diamines and phenol, low whipping speed is that under the condition of 200r/min～500r/min, the temperature rise rate with 2 ℃/min～5 ℃/min is warming up to 80 ℃～85 ℃ from room temperature, the rate of addition of 60/min～100 droplet/min of take again adds the formalin that massfraction is 37%, and be back flow reaction 2h～3h at 80 ℃～85 ℃ in temperature, obtain intermediate reaction product;
2., in intermediate reaction product, add ether amine again, the rate of addition of 60/min～100 droplet/min of take again adds the formalin that massfraction is 37%, then from temperature, be 80 ℃～85 ℃ and be warming up to 100 ℃～105 ℃, and be back flow reaction 3h～4h at 100 ℃～105 ℃ in temperature, the reaction solution after being refluxed; Control again vacuum tightness to more than 0.09MPa, the reaction solution after refluxing is carried out to decompression dehydration, when liquidus temperature reaches 120 ℃, stop decompression dehydration, obtain phenol aldehyde modified amine hardener;
The methyl cyclohexane diamines of step described in 1. with the molar mass of phenol than being (0.9～1.1): 1;
The methyl cyclohexane diamines of step described in 1. with the molar mass of formaldehyde than being (0.9～1.1): 1;
Step 2. described ether amine is one or more the mixture in EDR-104, EDR-176, D-230, T-403, XTJ-435 and XTJ-436;
Step 1. the molar mass of described methyl cyclohexane diamines and the step ether amine described in 2. than being 1:(1.9～2.1);
The mass ratio of the formalin that the formalin that the massfraction of step described in is 1. 37% and the step massfraction described in is 2. 37% is 1:2.
8. the preparation method of a kind of Novel epoxy reins adhesive according to claim 1, is characterized in that described silane coupling agent is KH560, KH580 or KH590.
9. the preparation method of a kind of Novel epoxy reins adhesive according to claim 1, under the condition that to it is characterized in that in room temperature and stirring velocity be 60r/min～120r/min, mark mixes 120 parts～130 parts PU-20 polyurethane modified epoxy resins, 0.5 part～2 parts silane coupling agents and 40 parts～100 parts phenol aldehyde modified amine hardeners by weight, stir 10min～12min, obtain liquid sizing agent; Again liquid sizing agent is at 25 ℃, to solidify 7d～10d or is at 80 ℃, to solidify 3h～4h in temperature in temperature, obtain Novel epoxy reins adhesive.
10. the preparation method of a kind of Novel epoxy reins adhesive according to claim 1, under the condition that to it is characterized in that in room temperature and stirring velocity be 60r/min～120r/min, mark mixes 120 parts of PU-20 polyurethane modified epoxy resins, 20 parts of epoxy resin E-51,30 parts of E-44,1 part of silane coupling agent and 80 parts of phenol aldehyde modified amine hardeners by weight, stir 10min～12min, obtain liquid sizing agent; Again liquid sizing agent is at 25 ℃, to solidify 7d～10d or is at 80 ℃, to solidify 3h～4h in temperature in temperature, obtain Novel epoxy reins adhesive.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885754A (en) * | 2016-05-03 | 2016-08-24 | 上海大学 | Low-temperature type flame retardant epoxy resin adhesive and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153978A (en) * | 2011-03-11 | 2011-08-17 | 中南林业科技大学 | Room-temperature solidification heat-resistant epoxy adhesive |
| WO2012021258A1 (en) * | 2010-08-10 | 2012-02-16 | 3M Innovative Properties Company | Epoxy structural adhesive |
-
2014
- 2014-08-01 CN CN201410376972.0A patent/CN104140782A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012021258A1 (en) * | 2010-08-10 | 2012-02-16 | 3M Innovative Properties Company | Epoxy structural adhesive |
| CN102153978A (en) * | 2011-03-11 | 2011-08-17 | 中南林业科技大学 | Room-temperature solidification heat-resistant epoxy adhesive |
Non-Patent Citations (1)
| Title |
|---|
| 赵明: "酚醛改性聚醚胺环氧树脂固化剂性能研究", 《万方数据库》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885754A (en) * | 2016-05-03 | 2016-08-24 | 上海大学 | Low-temperature type flame retardant epoxy resin adhesive and preparation method thereof |
| CN105885754B (en) * | 2016-05-03 | 2019-10-11 | 上海大学 | Low form fire retarding epoxide resin adhesive and preparation method thereof |
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Application publication date: 20141112 |