CN109517126A - A kind of polyurethane modified epoxy resin diluent and the low viscosity high-toughness epoxy resin composition being made from it - Google Patents
A kind of polyurethane modified epoxy resin diluent and the low viscosity high-toughness epoxy resin composition being made from it Download PDFInfo
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- CN109517126A CN109517126A CN201811382524.6A CN201811382524A CN109517126A CN 109517126 A CN109517126 A CN 109517126A CN 201811382524 A CN201811382524 A CN 201811382524A CN 109517126 A CN109517126 A CN 109517126A
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- epoxy resin
- diluent
- polyurethane modified
- temperature
- polyurethane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Abstract
The present invention relates to a kind of polyurethane modified epoxy resin diluents and the low viscosity high-toughness epoxy resin composition being made from it, the preparation method of the polyurethane modified epoxy resin diluent to include the following steps: to measure the hydroxyl value in the epoxy resin diluent containing hydroxyl；Under nitrogen atmosphere, MDI is added in epoxy resin diluent according to the stoichiometric ratio that isocyano can react completely with the hydroxyl in diluent, stirs, temperature of reaction system is made to be warming up to 110~130 DEG C, 4~6h is kept the temperature, polyurethane-modified epoxy resin diluent is obtained.Gained polyurethane modified epoxy resin diluent of the invention has preferable dilution effect to epoxy resin, and elongation at break, bending strain greatly improve after the epoxy resin composition of composition, tensile strength, bending strength, bending modulus are to occur declining to a great extent accordingly simultaneously, show as apparent toughness enhancing.
Description
Technical field
The present invention relates to Epoxy Resin Technology fields, and in particular to a kind of polyurethane modified epoxy resin diluent and by it
The low viscosity epoxy resin compositions of composition.
Background technique
669 common epoxy resin diluent main component is ethylene glycol diglycidylether, epoxide number in the market
For 0.6-0.7, its epoxide number is such as calculated according to the structure of ethylene glycol diglycidylether, then should be 1.14, the two difference compared with
Greatly, it traces it to its cause, may be urged in its production process using the acid of mainstream due to ethylene glycol diglycidylether enterprise in the market
Change two-step method, the continuous addition side reaction in first step reaction is difficult to control, so that except generation ethylene glycol when the second one-step hydrolysis
Outside diglycidyl ether, there are also the epoxy terminated products containing polyhydroxy on other a large amount of main chains, and fail to count according to chemistry
One glycidol ether of ethylene glycol and ethylene glycol of quantitative response etc., reduces the epoxide number of product.For this phenomenon, the present invention couple
Such epoxy resin diluent is modified, and so that it is not only played dilution effect to composition epoxy resin, simultaneously
The cured product made has preferable toughness.
Summary of the invention
The purpose of the present invention is to provide a kind of polyurethane modified epoxy resin diluents, not only to composition epoxy resin
The cured product for playing dilution effect, while making has preferable toughness.
The present invention solves scheme used by above-mentioned technical problem:
A kind of preparation method of polyurethane modified epoxy resin diluent, includes the following steps:
(1) hydroxyl value in the epoxy resin diluent containing hydroxyl is measured；
(2) under nitrogen atmosphere, the stoichiometric ratio that can be reacted completely with the hydroxyl in diluent according to isocyano
MDI is added in epoxy resin diluent, is stirred, temperature of reaction system is made to be warming up to 110~130 DEG C, 4~6h is kept the temperature, obtains
To polyurethane-modified epoxy resin diluent.
Preferably, the epoxy resin diluent includes: 669 epoxy resin diluents.
Preferably, step (1) is using the hydroxyl value in acetic anhydride-sulfuric acid process measurement epoxy resin diluent.
Preferably, temperature-rise period in step (2) are as follows: risen to temperature of reaction system by room temperature with the speed of 2~3 DEG C/min
120℃。
Preferably, MDI and epoxy resin is added according to n (NCO): n (OH)=1:1 ratio in step (2).
The present invention also provides a kind of polyurethane modified epoxy resin diluents, are prepared into using above-mentioned preparation method
It arrives.
The present invention also provides application of the above-mentioned polyurethane modified epoxy resin diluent in epoxy resin cure,
In, the weight ratio of the polyurethane modified epoxy resin diluent and epoxy resin is 3:7~8:2.
The present invention also provides a kind of low viscosity high-toughness epoxy resin composition, the component including following parts by weight:
Epoxy resin, 20~70 parts；
Diluent, 80~30 parts；
Curing agent, 25 parts；
Curing accelerator, 0.5 part, wherein the diluent is that polyurethane modified epoxy resin obtained by above-mentioned preparation method is dilute
Release agent or above-mentioned polyurethane modified epoxy resin diluent.
Preferably, the ratio of the epoxy resin and diluent is 7:3~6:4.
Preferably, the epoxy resin includes bisphenol A epoxide resin, bisphenol F epoxy resin, novolac epoxy resin, shrink
One or more of glycerol ester type epoxy resin mixture；The curing agent include cyanoethylation triethylene tetramine, ethylenediamine,
Diethylenetriamine, triethylene tetramine, polyethylene polyamine；The curing accelerator includes DMP30, DMP20, benzyl dimethylamine, 2-
Methylimidazole.
By the small molecule reaction of hydroxyl in the isocyano and diluent in MDI, molecule is integrally carried out to diluent
Chain chain extension, molecular weight increase, and it is more preferable that the modified more former diluent of diluent is added to cured product toughness in epoxy resin；
Contain phenyl ring in MDI, is introduced into after diluent and increases the heat resistance and intensity of curing system；Improve the epoxy of diluent
Value, so that the intensity of cured product is higher.
Gained polyurethane modified epoxy resin diluent of the invention has preferable dilution effect to epoxy resin, and forms
Epoxy resin composition after elongation at break, bending strain greatly improve, while tensile strength, bending strength, bending
Modulus is to occur declining to a great extent accordingly, shows as apparent toughness enhancing.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawings, but the embodiment in attached drawing is not constituted to any limit of the invention
System.
Fig. 1 is the reaction principle of the embodiment of the present invention polyurethane-modified 669；
Fig. 2 is the viscosity of mixed system in the embodiment of the present invention with the variation diagram of UE6M content；
Fig. 3 is 669, UE6M, N-TETA and epoxy resin-cured product infrared test result in the embodiment of the present invention；
Fig. 4 is the epoxy resin cured product fissipation factor variation with temperature figure of different compositions in the embodiment of the present invention；
Fig. 5 is that the tensile strength of the epoxy resin cured product of different compositions and elongation at break become in the embodiment of the present invention
Change；
Fig. 6 is the shore D hardness that different ratio UE6M dilutes epoxy-resin systems in the embodiment of the present invention.
Specific embodiment
For a better understanding of the present invention, the following examples are to further explanation of the invention, but the contents of the present invention
It is not limited solely to the following examples.
The preparation of polyurethane-modified 669 diluent:
It uses acetic anhydride-sulfuric acid process to measure 669 hydroxyl value range as 0.06-0.10, is placed in three mouthfuls for removed water 669
In flask, the steamed MDI of weight is placed in constant pressure separatory funnel, slowly drips it according to n (NCO): n (OH)=1:1 ratio
It is added in the three-necked flask for filling 669, the stirring rate of blender is 200rpm in there-necked flask, leads to N2Protection adjusts reaction temperature
Degree makes temperature of reaction system slowly be warming up to 120 DEG C from room temperature, keeps the temperature 4h, obtains reaction product.Fig. 1 is polyurethane of the present invention
Modified 669 reaction principle.
Epoxy resin samples preparation:
By MDI modified 669 (UE6M), epoxy resin CYD-128 (E51), curing agent cyanoethylation triethylene tetramine (N-
TETA), curing accelerator DMP30 etc. in a reservoir with glass bar be sufficiently stirred until system be uniformly mixed, will mix at room temperature
It closes object and stirs 1h under vacuum conditions with the bubble in removing system, after being disposed, be cast in Teflon mould, put
Enter baking oven and be warming up to 30 DEG C, be warming up to 60 DEG C after keeping the temperature 20h, keep the temperature 8h, system sufficiently solidifies, and demoulding obtains consolidating for epoxy resin
Change product.The present embodiment has prepared the mixed system of 6 components, and the epoxy resin-cured product materials of different systems match such as table
Shown in 1.
The UE6M/E51/N-TETA/DMP30 dosage of 1 different ratio of table
MDI modified 669 and epoxy resin mixed system viscosity test:
According to experimental method specified in GB/T 22314-2008 " measurements of plastics, epoxy resin viscosity ", MDI is changed
After mixing according to ratio shown in table 1, using NDJ-8S type Digital Viscometer, (tech is helped in Shanghai for property 669 and epoxy resin
Instruments and meters Co., Ltd) viscosity of mixed system to be tested, test temperature is 25.0 DEG C.Test results are shown in figure 2.
In figure as can be seen that after UE6M diluent is added, epoxy resin mixed system viscosity declines clearly, works as mixing
When the mass ratio of UE6M and E51 epoxy resin is 3:7 in system, system viscosity is only 762 mPas, only E51 epoxy resin
The 6.35% of viscosity, as the dosage of UE6M in mixed system is continuously increased, epoxy resin mixed system viscosity constantly declines, when
When the mass ratio of UE6M and E51 epoxy resin is 4:6, the viscosity of epoxy resin mixed system have declined to only
172mPas, close to the viscosity of pure UE6M, it is seen then that epoxy resin diluent obtained by the present embodiment has very epoxy resin
Excellent dilution effect.
Infrared test:
669 and MDI are changed using Fourier infrared spectrograph (TENSOR II, Brooker (Beijing) Science and Technology Ltd.)
Property 669 is measured, measuring resolution 4cm-1, scanning times are 16 times, test scope 400-4000cm-1, test result
As shown in Figure 3.
The infared spectrum of UE6M is in 2270cm-1Nothing-NCO characteristic peak, and 3300cm-1And 1730cm-1There is absorption peak in place,
Show that the MDI being added in 669 is sufficiently reacted with-the OH in 669, generates the feature structure with carbamate
UE6M；Simultaneously in 3500cm-1- OH the absorption peak strength at place declines to a great extent, and demonstrates reacting for-OH in 669 and MDI.Using
In the infrared spectrum of the diluted E51 epoxy resin of the cured UE6M of N-TETA, in 1730cm-1There is carbonyl identical with UE6M in place
Base absorption peak shows there is carbamate structures in cured product；The selected characteristic absorption peak 1600cm of box-1、
1580cm-1、1500cm-1And 1450cm-1For the characteristic absorption peak band of phenyl ring, show that diluent UE6M contains with cured product
There is phenyl ring.
Dynamic thermo-mechanical analsis:
Use the dynamic mechanical temperature of dynamic thermomechanical analysis apparatus (DMA1, Mei Tele-support benefit) measurement solidified sample
Spectrum.Mode determination is chosen to be stretch mode, test frequency 1Hz, 5 DEG C/min of heating rate, -30 DEG C of temperature scanning range -150
℃.Test results are shown in figure 4.Due to still containing a large amount of aliphatic carbon chain flexible linked by ehter bond in UE6M,
The glass transition temperature of solidfied material is low compared with the glass transition temperature of E51 solidfied material, therefore UE6M in epoxy resin mixed system
Ingredient is more, and the glass transition temperature of cured product is lower.Wherein UE6M-1, UE6M-2, UE6M-3, UE6M-4, UE6M-5
Five kinds of cured product fissipation factor figures in only there is single absorption peak, illustrate that N-TETA is solid since UE6M is similar to E51 structure
Both the UE6M rubber phase that change generates and E51 epoxy resin-base compatibility are preferable.But in the curing system ingredient of UE6M after
Continuous when increasing, when the mass fraction of UE6M in mixed system reaches 80%, architecture is inverted, and solidifies in mixed system
UE6M as the matrix in cured product, E51 epoxy resin cured product is the dispersed phase in cured product, the compatible portion of the two
Divide and form a phase, corresponds to the absorption peak on dynamic mechanical map at 60 DEG C；120 DEG C or so appearance on this system dynamic mechanical map
Another fissipation factor peak corresponds to the absorption peak of the second phase E51 epoxy resin-cured product.
Tensile strength and elongation at break test:
It is wanted by GB/T 528-2009 " measuring method of vulcanized rubber or thermoplastic elastomer tensile stress-strain performance " standard
The casting dumb-bell shape tensile sample in polytetrafluoro mold is sought, according to test method specified in GB/T 528-2009, use is omnipotent
Tensile testing machine (CMT4204, Mei Tesi industrial system (China) Co., Ltd) tests its tensile strength, elongation at break, if
The movement speed of clamp holder is 5cm/min.Test results are shown in figure 5, it can be seen from the figure that UE6M-1 and UE6M-2
Viscosity is only the 6.35% and 1.43% of UE6M-0, but its tensile strength is respectively 87.9% He of UE6M-0 solidfied material
80.9%, in 60MPa or more, elongation at break is 8 times of UE6M-0 or more, it is known that through the diluted epoxy resin of UE6M
Compared with pure epoxy resin system in the case where tensile strength is held essentially constant, viscosity declines to a great extent system, and presents good
Toughness.
Bending property test:
Long strip type is poured in polytetrafluoro mold by GB/T 9341-2008 " measurement of plastics bending property " standard requirements
Sample uses universal tensile testing machine (CMT4204, Mei Tesi industry according to test method as defined in GB/T 9341-2008
System (China) Co., Ltd) tested, instrument software kit provide test report in read sample bending strength,
The parameters such as bending strain and bending modulus set the movement speed of clamper as 5cm/min.Diluent UE6M in mixed system
Influence of the dosage to cured product bending property it is as shown in table 2.
Using UE6M to compared with pure epoxy resin system, the toughening effect of cured product compares after epoxy resin dilution
Obviously, component number is the curing system of UE6M-2, and bending strength is number UE6M-0 pure epoxy resin cured product
74%, bending modulus is the 90.3% of pure epoxy resin cured product, and bending strain is its 2 times, it is seen that polysulfide rubber is to epoxy
The toughening effect of resin clearly, shows through the cured UE6M cured product of DMP30 and through the cured E51 asphalt mixtures modified by epoxy resin of DMP30
Both rouge solidfied materials compatibility is preferable, and in suitable proportional region, the two can form highly uniform " sea-island " structure.
Bending strength, bending modulus and the bending strain of 2 different component cured product of table.
Hardness test:
According to GB/T 531.1-2008 " vulcanized rubber or thermoplastic elastomer penetration hardness test method part 1: shore
Hardometer method (Shao Er hardness) " specified in measuring method, using shore D hardometer, (KHL810A, Wuhan Kurt science and technology have
Limit company) sample is measured, measurement result is as shown in Figure 6.
In conclusion modified epoxy resin diluent has the feature structure of carbamate, it will be in former diluent
Free epoxy terminated oligomer carries out chain extension, and the degree of functionality of epoxy group is improved compared with commercially available diluent.Modified diluent
There is preferable dilution effect to epoxy resin, and due to more similar to epoxy resin structural, the product that the two solidifies
Compatibility is preferable.Tensile strength, bending strength, bending modulus, the hardness of solidfied material are on a declining curve, but because flexible chain increases
More, the elongation at break of system and bending strain are significantly increased, and show as toughness raising.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of polyurethane modified epoxy resin diluent, which comprises the steps of:
(1) hydroxyl value in the epoxy resin diluent containing hydroxyl is measured；
It (2) under nitrogen atmosphere, can be with stoichiometric ratio that the hydroxyl in diluent reacts completely by MDI according to isocyano
It is added in epoxy resin diluent, stirs, temperature of reaction system is made to be warming up to 110~130 DEG C, keep the temperature 4~6h, obtain poly- ammonia
Ester modified epoxy resin diluent.
2. preparation method according to claim 1, which is characterized in that the epoxy resin diluent includes: 669 asphalt mixtures modified by epoxy resin
Rouge diluent.
3. preparation method according to claim 1, which is characterized in that step (1) measures ring using acetic anhydride-sulfuric acid process
Hydroxyl value in oxygen diluent resin.
4. preparation method according to claim 1, which is characterized in that temperature-rise period in step (2) are as follows: with 2~3 DEG C/min
Speed temperature of reaction system is risen to 120 DEG C by room temperature.
5. a kind of polyurethane modified epoxy resin diluent, which is characterized in that use the described in any item systems of Claims 1 to 4
Preparation Method is prepared.
6. application of the polyurethane modified epoxy resin diluent in epoxy resin cure, feature described in claim 5 exist
In the weight ratio of the polyurethane modified epoxy resin diluent and epoxy resin is 3:7~8:2.
7. a kind of low viscosity high-toughness epoxy resin composition, which is characterized in that the component including following parts by weight:
Epoxy resin, 20~70 parts；
Diluent, 80~30 parts；
Curing agent, 25 parts；
Curing accelerator, 0.5 part, wherein the diluent is polyurethane-modified obtained by any one of Claims 1 to 4 preparation method
Epoxy resin diluent, or be the polyurethane modified epoxy resin diluent described in claim 5.
8. composition epoxy resin according to claim 7, which is characterized in that the ratio of the epoxy resin and diluent
For 7:3~6:4.
9. composition epoxy resin according to claim 7, which is characterized in that the epoxy resin includes bisphenol-A epoxy
One or more of resin, bisphenol F epoxy resin, novolac epoxy resin, glycidyl ester type epoxy resin mixture；It is described
Curing agent includes cyanoethylation triethylene tetramine, ethylenediamine, diethylenetriamine, triethylene tetramine, polyethylene polyamine；The solidification
Promotor includes DMP30, DMP20, benzyl dimethylamine, 2-methylimidazole.
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Cited By (2)
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| CN113845789A (en) * | 2021-08-26 | 2021-12-28 | 宁波爱甬新材料科技有限公司 | Super-weather-resistant powder coating with uniform surface texture and preparation method thereof |
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| CN113845789A (en) * | 2021-08-26 | 2021-12-28 | 宁波爱甬新材料科技有限公司 | Super-weather-resistant powder coating with uniform surface texture and preparation method thereof |
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| CN109517126B (en) | 2021-05-18 |
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