CN109880171A - Have effects that toughening and reduces the double epoxy resin additive of solidification temperature and its preparation, application method - Google Patents
Have effects that toughening and reduces the double epoxy resin additive of solidification temperature and its preparation, application method Download PDFInfo
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Abstract
The present invention relates to a kind of epoxy resin additive for having effects that toughening and reducing solidification temperature pair and its preparations, application method.Nano-TiO has been prepared in hydrolysis cosolvent using sol-gel method first2Colloidal sol then carries out it with titanate coupling agent in-situ modified to obtain modified Nano TiO2Colloidal sol, the cosolvent finally to dissolve each other with energy and colloidal sol, epoxy prepolymer are uniformly mixed, and so far complete the preparation of epoxy resin additive.The additive is uniformly mixed with epoxy prepolymer when use, solidifies crosslinking after removing solvent.The present invention efficiently solves nano-TiO2Particle is in high viscosity resins the problem of difficult dispersion, and the epoxy resin impact flexibility after solidification improves several times, and toughening effect is significant, while solidification temperature has dropped 30-40 DEG C, and 100 DEG C of gelation times shorten nearly half.
Description
Technical field
The present invention relates to rubber and plastic additive technology fields, and in particular to one kind has effects that toughening and reduces solidification temperature pair
Epoxy resin additive and its preparation, application method.
Background technique
Epoxy resin (Epoxide resin, EP) is most widely used a kind of matrix tree in polymer matrix composite
Rouge.Epoxy resin has the advantage that as important universal thermosetting resin 1. for a variety of clung bodies with good
Cementability；2. cure shrinkage is small；3. not generating gas in the curing process；4. heat resistance, resistance to chemical reagents are excellent；5. having excellent
Good durability；6. creep properties is small under certain load, (Liu Fangbiao, wangdan is brave, and Chen Yiwei particle enhances, is epoxy resin toughened
Based composites Progress In Preparation [J] Materials Science and Engineering journal, 2014,32 (4): 614-624.).Based on above-mentioned excellent
Point, epoxy resin is widely used to the various fields such as machinery, electronic apparatus, aerospace, communications and transportation and building at present.Often
It is in cross-linked structure after epoxy resin cure, has many advantages, such as that rigidity is big, hardness is high, but that there is also brittleness simultaneously is larger
The shortcomings that, thus epoxy resin is greatly limited in the application of high-technology field.In addition to this, epoxy resin is also
There are solidification temperatures it is higher, the curing reaction time is longer the problems such as, many researchers are attempted in epoxy-resin systems thus
It is middle that various promotors are added.How to epoxy resin carry out toughening modifying, making it, rapid curing is always asphalt mixtures modified by epoxy resin at room temperature
The research emphasis and hot spot of rouge.
There are many method for toughening of epoxyn, such as the modification of heat-resistant powder filler toughening, Toughened With High Performance Thermoplastics,
Nano-particle toughening modification, liquid crystal polymer toughening modifying etc..In these methods, although heat-resistant powder filler toughener can be with
The toughness of epoxy resin, but the liquid rubber as toughener are increased substantially, since intensity itself, rigidity, heat resistance are lower
Cause modified material system intensity, rigidity and heat resistance to reduce, and can also generate in epoxy matrix solidification process point
Phase does not have obvious effect (such as promotion) to the curing cross-linking reaction of epoxy resin-base.Though Toughened With High Performance Thermoplastics modifying agent
So can to avoid problem in terms of system intensity, rigidity existing for heat-resistant powder filler plasticized modifier and heat resistance, but its
Body is to the curing cross-linking reaction of epoxy resin-base also without obvious effect (facilitation is not present).Liquid crystal polymer toughening changes
Although property agent has the function of significantly improving epoxy matrix toughness and intensity and promotes curing reaction, its cost is too high,
Be not suitable for industrial production.Nano-particle toughening modifying agent, which has, increases substantially epoxy resin toughness without dropping low intensive spy
Point, and the curing reaction of epoxy resin-base can be obviously promoted, it is most important that simple process is easy to operate, at low cost, tool
There is preferable industrial production application prospect.Compared with other nanoparticles, nano-TiO2In Ti be located at IV B of the periodic table of elements
Race has 3d electronics and unoccupied orbital, and chemical property is more active, and easily the oxygen with the epoxy group with lone pair electrons reacts,
The interface binding power with epoxy resin is enhanced, thus toughening effect is than more significant.Nano-TiO at present2It is chiefly used in thermoplastic resin
Rouge, application is seldom in thermosetting resin (such as epoxy resin).
However nanoparticle surface can be higher, excessive or dispersion can generate agglomeration when uneven, and then influence
The mechanical property of material.Common nanoparticle dispersing method has Direct dispersion method, in-situ dispersion polymerization method, sol-gel method.
Direct dispersion method is to prepare hybrid material most straightforward approach, suitable for the nanoparticle of various forms, since nanoparticle is deposited
In the easily spontaneous reunion of very big interfacial free energy, inorganic nano-particle and polymer cannot be eliminated using conventional blend method
High interface between matrix can be poor, therefore needs to carry out it using coupling agent surface mostly and be modified, and enhancing nanoparticle is poly-
The interface compatibility in object is closed, keeps nanoparticle evenly dispersed in the polymer.In-situ dispersion polymerization method needs first by nanoparticle
It is uniformly mixed with polymer monomer, then causes monomer polymerization under proper condition.Similar with blending method, nanoparticle is being dispersed
The problem of there is also reunions in system need to carry out surface and be modified, the modified nanoparticle in surface energy in polymer monomer
It is evenly dispersed and keep nanoscale and characteristic.In-situ dispersion polymerization method can a polymerization forming, be suitable for all kinds of monomers, can
Keep the superperformance of hybrid.Sol-gel method is that under certain condition, the predecessors such as alcoxyl metal or metal salt are hydrolyzed
It is condensed into colloidal sol, then volatilizees or heats through solvent, colloidal sol is made to be converted into the process of the oxide gel of reticular structure.Colloidal sol-
Gel method is a kind of important method for preparing hybrid material.If nanoparticle is directly mixed with high polymer or high polymer presoma,
Since the reunion of nanoparticle may generate mutually separation to lose nano effect, the hydridization prepared using sol-gel method
A possibility that material then inhibits nanoparticle mutually to separate, with the microtexture of nano hybridization in the structure of material, and
Stability thermodynamically.In addition sol-gel method reaction condition is mild, is easy to control, and material adjusting leeway is big, passes through change
The organic and inorganic constituent content for participating in reaction is easily achieved the performance cutting of Inorganic-Organic Hybrid Material, obtains required performance
Material.
Summary of the invention
One of the objects of the present invention is to provide a kind of epoxy resin for having effects that toughening and reducing solidification temperature pair to add
Add the preparation method of agent, comprising the following steps: (a) prepares nano-TiO using sol-gel method2Colloidal sol；(b) titanate esters are utilized
Coupling agent is to nano-TiO2Colloidal sol is modified, and obtains modified Nano TiO2Colloidal sol, as target product --- double effect asphalt mixtures modified by epoxy resin
Fat additives.
Further, step (a) prepares nano-TiO2The method of colloidal sol is specific as follows: by alcoholic co-solvent, hydrolyzation catalysis
Agent is placed in water to obtain mixture, and titanium source is added dropwise into mixture under stirring, obtains nano-TiO2Colloidal sol.
Wherein, alcoholic co-solvent is selected from least one of methanol, ethyl alcohol, propyl alcohol, butanol, isopropanol, ethylene glycol, hydrolysis
Any one of catalyst in citric acid, acetic acid, dilute hydrochloric acid, titanium source are specially tetraethyl titanate.
Further, react needed for alcoholic co-solvent, hydrolyst, titanium source volume ratio be 1-5:0.1-2:1, water
Dosage is equivalent to 1-6 times of titanium source mole.
Further, step (b) prepares modified Nano TiO2The method of colloidal sol is specific as follows: titanate coupling agent is added dropwise
To nano-TiO2In colloidal sol, adds organic ketone cosolvent and be uniformly mixed.
Wherein, titanate coupling agent is selected from titanate esters TTS, pyrophosphate titanate esters, bis- (two octyloxy pyrophosphoric acid ester groups)
Ethylene titanate esters, tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters, in three oleic acid acyloxy titanate esters of isopropyl
Any one, organic ketone cosolvent is selected from acetone, methyl ethyl ketone, cyclohexanone, butanone, methyl iso-butyl ketone (MIBK), isophorone, dipropyl
At least one of keto-alcohol.
Further, the dosage of titanate coupling agent is equivalent to the 1%-5% of titanium source quality, the use of organic ketone cosolvent
Amount is equivalent to the 3%-5% of epoxy resin quality.
Another object of the present invention is to provide the epoxy resin additives that one kind is prepared according to the method described above, this adds
Adding agent to be added in epoxy resin has toughening and reduction solidification temperature double effects.
Third of the invention is designed to provide a kind of epoxy resin for having effects that toughening and reducing solidification temperature pair again
The application method of additive, specifically includes the following steps: epoxy resin additive obtained is mixed with epoxy prepolymer
Uniformly, the remaining solvent of removing system obtains modified epoxy prepolymer, adds curing agent and other auxiliary agents, is uniformly mixed
?.
Further, the epoxy prepolymer is specially bisphenol A type epoxy resin, the trade mark E-55, E-51, E-
44, any one in E-42, E-35, E-31.The curing agent is selected from aliphatic diamine or polyamines, aromatic polyamine, modification
At least one of fatty amine, organic acid, acid anhydrides, modified amine curing agent DQ204H, polyamide.
Further, the mode for removing system residual solvent is to be evaporated under reduced pressure, 50-100 DEG C of temperature, pressure 0.05MPa-
0.3MPa, time 60-100min.
The present invention prepares double effect epoxy resin additives one and is divided into two steps.The hydrolysis cosolvent that the first step uses can be with
It dissolves each other with presoma tetraethyl titanate, deionized water, can tetraethyl titanate and deionized water be diluted and be uniformly mixed；Furthermore
Also there is inhibiting effect to hydrolysis, guarantees that hydrolysis slowly carries out, to obtain nano-TiO2Colloidal sol.Second step titanate esters idol
Join agent to the nano-TiO in colloidal sol2Particle progress is in-situ modified, and then it dissolves each other with energy and colloidal sol, epoxy prepolymer
Organic ketone cosolvent be uniformly mixed, obtain modified Nano TiO2Colloidal sol, i.e., double effect epoxy resin additives.Gained addition
TiO in agent product2The average grain diameter of particle is 9.4nm.Double effect epoxy resin additives are in use, organic ketone contained therein
Class cosolvent energy and nano-TiO2Hydrolysis cosolvent, epoxy prepolymer in colloidal sol dissolve each other, and thus overcome colloidal sol and ring
The problem of oxygen resin prepolymer poor compatibility, guarantees the two good mixing, so that system is limpid, no phase separation.Vacuum distillation removes
The transparent state of epoxy prepolymer after solvent, effectively by the nano-TiO in modified colloidal sol2Particle is distributed to asphalt mixtures modified by epoxy resin
In rouge prepolymer, and it is evenly dispersed with nanoscale, and last resolidification crosslinking can obtain high-toughness epoxy resin material.
Compared with prior art, the invention has the following advantages:
(1) nano-TiO is solved2Particle is easy to reunite in high viscosity resins, disperses non-uniform problem, and detection shows
Modified nano-TiO2Nano-TiO in colloidal sol2Average particle size is 9.4nm, with nanoscale in epoxy resin-base
It is evenly dispersed.
(2) double effect epoxy resin additives first are prepared with sol-gel method, then adds it to epoxy prepolymer
In it is modified, this charging process overcomes that energy consumption existing for nanoparticle Direct dispersion method is high, time-consuming, dispersion is uneven
It is even and the disadvantages of in-situ dispersion polymerization method raw material is various, process reaction is difficult to control, have that technical process is simple, independent, easy behaviour
Make, equipment requirement it is low, the advantages such as can be mass-produced.
(3) the epoxy resin impact flexibility after solidifying improves 4.5 times or so (108KJ/m2), toughening effect is significant, produces
Product tensile strength, bending strength not only increase without decline instead, and low intensive ask can be dropped by overcoming most method for toughening
Topic.
(4) nano-TiO2Particle makes epoxy resin cure exothermic peak temperature be lower, and curing activation energy reduces；With it is unmodified
Epoxy resin is compared, and modified epoxy resin cure exothermic peak beginning, summit, peak finishing temperature decline 30-40 DEG C or so；In phase
Nearly half is shortened with gelation time under solidification temperature, a large amount of energy consumptions can be reduced in production.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific
Embodiment is further described.
Source chemicals used in the present invention are common commercially available.
The tensile strength test of sample is carried out according to GB 1040-79 in the embodiment of the present invention, and bending strength is tested according to GB
1042-79 is carried out, and impact flexibility test is carried out according to GB 1043-79, and epoxy resin gel time test is according to GB
12007.7-1989 carrying out.Synchronous solving model STA449F3/STA449F3 used in heat analysis.
Embodiment 1
First in proportion by cosolvent 1 (0.9mL propyl alcohol), hydrolyst (dilute salt that 0.45mL mass fraction is 30%
Acid), (0.16g) is uniformly mixed in deionized water, then 0.5g tetraethyl titanate is added to according to the rate of addition of 1g/min
In said mixture, reaction is hydrolyzed in stirring 20min, obtains nano-TiO2Colloidal sol.
Then 0.01g titanate coupling agent (titanate esters TTS) is added to above-mentioned nano-TiO2In colloidal sol, 10min is stirred
It carries out in-situ modified, cosolvent 2 (5mL butanone) is added after the completion of modified and is uniformly mixed, prepared modified Nano is obtained
TiO2Colloidal sol, i.e. epoxy resin additive.
By prepared modified Nano TiO2Colloidal sol is added in 80g epoxy prepolymer (E-51 type epoxy resin),
Stirring 1h is uniformly mixed it, and 100min is then evaporated under reduced pressure under the conditions of 100 DEG C, 0.05MP, removes solvent and obtains modified ring
25g amine curing agent (modified amine curing agent is finally added in oxygen resin prepolymer into modified epoxy prepolymer
DQ204H it) is uniformly mixed, solidifies 7h at 100 DEG C.
Embodiment 2
First in proportion by cosolvent 1 (1.8mL propyl alcohol), hydrolyst (dilute salt that 0.9mL mass fraction is 30%
Acid), (0.32g) is uniformly mixed in deionized water, then 1.0g tetraethyl titanate is added to according to the rate of addition of 1g/min
In said mixture, reaction is hydrolyzed in stirring 20min, obtains nano-TiO2Colloidal sol.
Then 0.02g titanate coupling agent (titanate esters TTS) is added to above-mentioned nano-TiO2In colloidal sol, 10min is stirred
It carries out in-situ modified, cosolvent 2 (5mL butanone) is added after the completion of modified and is uniformly mixed, prepared modified Nano is obtained
TiO2Colloidal sol, i.e. epoxy resin additive.
By prepared modified Nano TiO2Colloidal sol is added in 80g epoxy prepolymer (E-51 type epoxy resin),
Stirring 1h is uniformly mixed it, and 100min is then evaporated under reduced pressure under the conditions of 100 DEG C, 0.05MP, removes solvent and obtains modified ring
25g amine curing agent (modified amine curing agent is finally added in oxygen resin prepolymer into modified epoxy prepolymer
DQ204H it) is uniformly mixed, solidifies 7h at 100 DEG C.
Embodiment 3
First in proportion by cosolvent 1 (2.7mL propyl alcohol), hydrolyst (dilute salt that 1.35mL mass fraction is 30%
Acid), (0.48g) is uniformly mixed in deionized water, then 1.5g tetraethyl titanate is added to according to the rate of addition of 1g/min
In said mixture, reaction is hydrolyzed in stirring 10min, obtains nano-TiO2Colloidal sol.
Then 0.03g titanate coupling agent (titanate esters TTS) is added to above-mentioned nano-TiO2In colloidal sol, 10min is stirred
It carries out in-situ modified, cosolvent 2 (5mL butanone) is added after the completion of modified and is uniformly mixed, prepared modified Nano is obtained
TiO2Colloidal sol, i.e. epoxy resin additive.
By prepared modified Nano TiO2Colloidal sol is added in 80g epoxy prepolymer (E-51 type epoxy resin),
Stirring 1h is uniformly mixed it, and 100min is then evaporated under reduced pressure under the conditions of 100 DEG C, 0.05MP, removes solvent and obtains modified ring
25g amine curing agent (modified amine curing agent is finally added in oxygen resin prepolymer into modified epoxy prepolymer
DQ204H it) is uniformly mixed, solidifies 7h at 100 DEG C.
Embodiment 4
First in proportion by cosolvent 1 (3.6mL propyl alcohol), hydrolyst (dilute salt that 1.8mL mass fraction is 30%
Acid), (0.64g) is uniformly mixed in deionized water, then 2.0g tetraethyl titanate is added to according to the rate of addition of 1g/min
In said mixture, reaction is hydrolyzed in stirring 20min, obtains nano-TiO2Colloidal sol.
Then 0.04g titanate coupling agent (titanate esters TTS) is added to above-mentioned nano-TiO2In colloidal sol, 10min is stirred
It carries out in-situ modified, cosolvent 2 (5mL butanone) is added after the completion of modified and is uniformly mixed, prepared modified Nano is obtained
TiO2Colloidal sol, i.e. epoxy resin additive.
By prepared modified Nano TiO2Colloidal sol is added in 80g epoxy prepolymer (E-51 type epoxy resin),
Stirring 1h is uniformly mixed it, and 100min is then evaporated under reduced pressure under the conditions of 100 DEG C, 0.05MP, removes solvent and obtains modified ring
25g amine curing agent (modified amine curing agent is finally added in oxygen resin prepolymer into modified epoxy prepolymer
DQ204H it) is uniformly mixed, solidifies 7h at 100 DEG C.
Control group
Cosolvent 2 (5mL butanone) is added in 80g epoxy prepolymer (E-51 type epoxy resin) first, is stirred
1h is uniformly mixed it, and 100min is then evaporated under reduced pressure under the conditions of 100 DEG C, 0.05MP, removes solvent and obtains modified epoxy tree
It is mixed that 25g amine curing agent (modified amine curing agent DQ204H) is finally added in rouge prepolymer into modified epoxy prepolymer
It closes uniformly, solidifies 7h at 100 DEG C.
Corresponding survey has been carried out according to above-mentioned relevant criterion to epoxy resin product made from embodiment 1-4 and control group
Examination, the results are shown in Table 1.
Table 1 solidify after epoxy resin samples mechanical property table
As can be seen from Table 1, the impact flexibility of blank control sample is 19.4KJ/m2, add a certain amount of provided by the invention
Modified Nano TiO2After colloidal sol, the impact flexibility of epoxy resin samples is increasing always, and impact flexibility maximum value is 108KJ/m2,
4.5 times are increased, toughening effect is very significant.
Equally compared with blank control sample, the tensile strength of epoxy resin product obtained by embodiment 1-4, bending strength are not only
Do not decline increased instead, this explanation can also enhance while toughening.This is because TiO2Nanoparticle has larger
Specific surface area, therefore add it in EP matrix, the active group on surface under the action of titanate coupling agent with EP points
Subchain effect, generates the active force for being greater than Van der Waals force, to form good interface cohesion with EP matrix.When system is by outer
Masterpiece used time, nanoparticle transmit power to surrounding, and induce in EP matrix and generate micro-crack (on the one hand absorbable a part
Energy, the crosslinking points that on the other hand also can be used as strand are hindered the extension of micro-crack), to reach the mesh of toughening
's.The additive amount very little of the epoxy resin additive, far below additive amount needed for General Physics blending method, this is fully demonstrated
Nanoscale TiO2Excellent fillibility, not needing very big dosage can make material be greatly improved in performance.
When having carried out DTA and gelation according to relevant criterion to epoxy resin product made from embodiment 1-4 and control group
Between (100 DEG C) test, as a result respectively as shown in table 2-3.
Table 2 solidify after epoxy resin samples DTA tables of data
Table 3 solidify after 100 DEG C of gelation time tables of data of epoxy resin samples
Blank control sample curing exothermic peak beginning, summit, peak finishing temperature are respectively 117,186,217 it can be seen from table 2,3
DEG C, 100 DEG C of gelation times are 122min；Add a certain amount of modified Nano TiO provided by the invention2It, at most can be with after colloidal sol
Make all 30-40 DEG C of the decline of curing exothermic peak beginning, summit, peak finishing temperature, gelation time shortens under identical solidification temperature
Nearly half.This is primarily due to nano-TiO2Ti has unoccupied orbital that can form co-ordination complex with epoxy group in particle, is catalyzed
Polymerization reaction.Furthermore the self-catalyzed reaction of epoxy resin be as caused by hydroxyl, and add nano-TiO2Surface has largely
Hydroxyl, it can be such that the crosslinking points of chemical reaction increase, therefore nano-TiO2The curing reaction temperature of epoxy resin can be reduced, shortened
Gelation time accelerates curing reaction speed.
Claims (10)
1. a kind of preparation method for having effects that toughening and reducing the double epoxy resin additive of solidification temperature, it is characterised in that packet
Include following steps:
(a) nano-TiO is prepared using sol-gel method2Colloidal sol；
(b) using titanate coupling agent to nano-TiO2Colloidal sol is modified, and obtains modified Nano TiO2Colloidal sol, this modification sol
As double effect epoxy resin additives.
2. preparation method as described in claim 1, it is characterised in that: step (a) prepares nano-TiO2The method of colloidal sol is specifically such as
Under: alcoholic co-solvent, hydrolyst are placed in water to obtain mixture, titanium source is added dropwise into mixture under stirring, obtains
To nano-TiO2Colloidal sol.
3. preparation method as claimed in claim 2, it is characterised in that: the alcoholic co-solvent be selected from methanol, ethyl alcohol, propyl alcohol,
At least one of butanol, isopropanol, ethylene glycol, the hydrolyst are any one in citric acid, acetic acid, dilute hydrochloric acid
Kind, the titanium source is specially tetraethyl titanate.
4. preparation method as claimed in claim 2, it is characterised in that: alcoholic co-solvent, hydrolyst, titanium source needed for reacting
Volume ratio be 1-5:0.1-2:1, the dosage of water is equivalent to 1-6 times of titanium source mole.
5. preparation method as described in claim 1, it is characterised in that: step (b) prepares modified Nano TiO2The method of colloidal sol has
Body is as follows: titanate coupling agent is added drop-wise to nano-TiO2In colloidal sol, adds organic ketone cosolvent and be uniformly mixed.
6. preparation method as claimed in claim 5, it is characterised in that: titanate coupling agent is selected from titanate esters TTS, pyrophosphate
Titanate esters, Di(dioctylpyrophosphato) ethylene titanate, tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters,
Any one in three oleic acid acyloxy titanate esters of isopropyl, organic ketone cosolvent are selected from acetone, methyl ethyl ketone, cyclohexanone, fourth
At least one of ketone, methyl iso-butyl ketone (MIBK), isophorone, diacetone alcohol；The dosage of titanate coupling agent is equivalent to titanium source matter
The 1%-5% of amount, the dosage of organic ketone cosolvent are equivalent to the 3%-5% of epoxy resin quality.
7. any one of -6 methods epoxy resin obtained for having effects that toughening and reducing solidification temperature pair adds according to claim 1
Add agent.
8. the application method of epoxy resin additive made from any one of -6 methods according to claim 1, it is characterised in that including
Following steps: epoxy resin additive is uniformly mixed with epoxy prepolymer, the remaining solvent of removing system is modified
Epoxy prepolymer adds curing agent and other auxiliary agents, is uniformly mixed.
9. application method as claimed in claim 8, it is characterised in that: the epoxy prepolymer is specially bisphenol-A type ring
Oxygen resin, any one in the trade mark E-55, E-51, E-44, E-42, E-35, E-31；The curing agent is selected from aliphatic two
Amine or polyamines, aromatic polyamine, modified fatty amine, organic acid, acid anhydrides, modified amine curing agent DQ204H, in polyamide extremely
Few one kind.
10. application method as claimed in claim 8, it is characterised in that: the mode for removing system residual solvent is vacuum distillation,
50-100 DEG C of temperature, pressure 0.05MPa-0.3MPa, time 60-100min.
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| CN116493053A (en) * | 2023-04-14 | 2023-07-28 | 山西普丽环境工程股份有限公司 | Regenerated denitration catalyst strengthening liquid and preparation method thereof |
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