CN109880171B - Epoxy resin additive with double effects of toughening and curing temperature reduction and preparation and use methods thereof - Google Patents
Epoxy resin additive with double effects of toughening and curing temperature reduction and preparation and use methods thereof Download PDFInfo
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Abstract
The invention relates to an epoxy resin additive with double effects of toughening and curing temperature reduction, and a preparation method and a use method thereof. Firstly, preparing nano TiO in a hydrolysis cosolvent by adopting a sol-gel method2Sol, then carrying out in-situ modification on the sol by using titanate coupling agent to obtain modified nano TiO2Finally, the sol is uniformly mixed with a cosolvent which can be mutually dissolved with the sol and the epoxy resin prepolymer, thereby completing the preparation of the epoxy resin additive. When in use, the additive is uniformly mixed with the epoxy resin prepolymer, and the mixture is cured and crosslinked after the solvent is removed. The invention effectively solves the problem of nano TiO2The particles are difficult to disperse in the high-viscosity resin, the impact toughness of the cured epoxy resin is improved by multiple times, the toughening effect is obvious, the curing temperature is reduced by 30-40 ℃, and the gelation time at 100 ℃ is shortened by nearly half.
Description
Technical Field
The invention relates to the technical field of rubber and plastic additives, in particular to an epoxy resin additive with double effects of toughening and curing temperature reduction, and a preparation method and a use method thereof.
Background
Epoxy resins (EP) are one of the most widely used matrix resins in polymer-based composites. As an important general-purpose thermosetting resin, an epoxy resin has the following advantages: the adhesive has good adhesion to various adherends; ② the curing shrinkage is small; no gas is generated in the curing process; fourthly, the heat resistance and the chemical resistance are excellent; fifthly, the product has excellent durability; sixthly, the creep property is small under a certain load (Liu Fang Biao, Wang Dang, Chen Yi. particle reinforced and toughened epoxy resin matrix composite material preparation research progress [ J ]. material science and engineering report, 2014,32(4): 614-624.). Based on the advantages, the epoxy resin is widely applied to various fields such as machinery, electronic and electric appliances, aerospace, transportation, buildings and the like. The common epoxy resin is in an crosslinked network structure after being cured, has the advantages of high rigidity, high hardness and the like, but also has the defect of high brittleness, so that the application of the epoxy resin in the high and new technical field is limited to a great extent. In addition, epoxy resins have problems of high curing temperature, long curing reaction time and the like, and for this reason, many researchers try to add various accelerators into epoxy resin systems. How to toughen and modify epoxy resin and make the epoxy resin rapidly cured at room temperature is always a research focus and a hot spot of epoxy resin.
The epoxy resin adhesive has many toughening methods, such as toughening of rubber elastomers, toughening and modification of thermoplastic resins, toughening and modification of nanoparticles, toughening and modification of liquid crystal polymers, and the like. In these methods, although the rubber-based elastomer toughener can greatly improve the toughness of the epoxy resin, the liquid rubber serving as the toughener has low strength, rigidity and heat resistance, so that the strength, rigidity and heat resistance of the modified material system are reduced, phase separation is generated in the curing process of the epoxy matrix, and the curing and crosslinking reaction of the epoxy matrix is not obviously affected (for example, accelerated). Although the thermoplastic resin toughening modifier can avoid the problems of system strength, rigidity and heat resistance existing in the rubber elastomer toughening modifier, the thermoplastic resin toughening modifier has no obvious effect (no promotion effect) on the curing and crosslinking reaction of an epoxy resin matrix. Although the liquid crystal polymer toughening modifier has the functions of obviously improving the toughness and the strength of an epoxy matrix and promoting a curing reaction, the cost is lowToo high to be suitable for industrial production. The nano particle toughening modifier has the characteristics of greatly improving the toughness of the epoxy resin without reducing the strength, can obviously promote the curing reaction of an epoxy resin matrix, and has the most important characteristics of simple process, easy operation, low cost and better industrial production application prospect. Nano TiO compared with other nanoparticles2The Ti in the epoxy resin is positioned in the IVB group of the periodic table of elements, has 3d electrons and empty orbitals, has more active chemical properties, is easy to react with oxygen of an epoxy group with lone pair electrons, and enhances the interface bonding force with the epoxy resin, so the toughening effect is more obvious. At present, nano TiO2Is mostly used for thermoplastic resins and is rarely used in thermosetting resins such as epoxy resins.
However, the nanoparticles have high surface energy, and when the nanoparticles are excessive or are unevenly dispersed, the nanoparticles can generate an agglomeration phenomenon, thereby influencing the mechanical properties of the material. The commonly used nanoparticle dispersion methods include a direct dispersion method, an in-situ dispersion polymerization method, and a sol-gel method. The direct dispersion method is the most direct method for preparing hybrid materials, is suitable for nano particles in various forms, and is very easy to spontaneously agglomerate due to the large interface free energy of the nano particles, and the high interface energy difference between inorganic nano particles and a polymer matrix cannot be eliminated by using a conventional blending method, so that the surface of the inorganic nano particles is mostly required to be modified by using a coupling agent, the interface compatibility of the nano particles in a polymer is enhanced, and the nano particles are uniformly dispersed in the polymer. The in-situ dispersion polymerization method is to mix the nano particles and the polymer monomer uniformly and then initiate the polymerization of the monomer under proper conditions. Similar to the blending method, the nanoparticles have the problem of agglomeration in a dispersion system, surface modification is needed, and the nanoparticles after surface modification can be uniformly dispersed in a polymer monomer and keep the nanoscale and the characteristics. The in-situ dispersion polymerization method can be used for one-step polymerization molding, is suitable for various monomers, and can keep the good performance of hybrids. The sol-gel method is a process of hydrolyzing and condensing precursors such as alkoxy metal or metal salt and the like into sol under a certain condition, and then volatilizing or heating the solvent to convert the sol into oxide gel with a network structure. The sol-gel method is an important method for preparing hybrid materials. If the nanoparticles are directly mixed with the high polymer or the high polymer precursor, the agglomeration of the nanoparticles may generate phase separation to lose the nano effect, the hybrid material prepared by the sol-gel method inhibits the possibility of phase separation of the nanoparticles, and the material has a nano hybrid microstructure and thermodynamic stability in the structure. In addition, the sol-gel method has mild reaction conditions, easy control and large material adjusting scope, and the performance cutting of the inorganic-organic hybrid material is easy to realize by changing the contents of organic and inorganic components participating in the reaction, so as to obtain the material with required performance.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of an epoxy resin additive with double effects of toughening and curing temperature reduction, which comprises the following steps: (a) preparation of nano TiO by sol-gel method2Sol; (b) use of titanate coupling agent to nano TiO2Modifying the sol to obtain modified nano TiO2The sol is the target product-dual-effect epoxy resin additive.
Further, the step (a) of preparing nano TiO2The sol method is as follows: putting alcohol cosolvent and hydrolysis catalyst into water to obtain a mixture, dropwise adding a titanium source into the mixture under the stirring state to obtain nano TiO2And (3) sol.
Wherein, the alcohol cosolvent is selected from at least one of methanol, ethanol, propanol, butanol, isopropanol and ethylene glycol, the hydrolysis catalyst is selected from any one of citric acid, acetic acid and dilute hydrochloric acid, and the titanium source is tetraethyl titanate.
Furthermore, the volume ratio of the alcohol cosolvent, the hydrolysis catalyst and the titanium source required by the reaction is 1-5:0.1-2:1, and the using amount of water is 1-6 times of the molar amount of the titanium source.
Further, preparing modified nano TiO in step (b)2The sol method is as follows: dripping titanate coupling agent into the nano TiO2Adding organic ketone cosolvent and mixing homogeneously.
Wherein the titanate coupling agent is selected from any one of titanate TTS, pyrophosphate titanate, bis (dioctyloxypyrophosphate) ethylene titanate, tetraisopropylbis (dioctylphosphite acyloxy) titanate and isopropyltrioleoxy titanate, and the organic ketone cosolvent is selected from at least one of acetone, methyl ethyl ketone, cyclohexanone, butanone, methyl isobutyl ketone, isophorone and diacetone alcohol.
Furthermore, the dosage of the titanate coupling agent is 1 to 5 percent of the mass of the titanium source, and the dosage of the organic ketone cosolvent is 3 to 5 percent of the mass of the epoxy resin.
Another object of the present invention is to provide an epoxy resin additive prepared by the above method, which has the dual effects of toughening and curing temperature reduction when added to an epoxy resin.
The invention further aims to provide a using method of the epoxy resin additive with double effects of toughening and curing temperature reduction, which specifically comprises the following steps: and (3) uniformly mixing the prepared epoxy resin additive and the epoxy resin prepolymer, removing the residual solvent of the system to obtain a modified epoxy resin prepolymer, adding the curing agent and other auxiliaries, and uniformly mixing.
Further, the epoxy resin prepolymer is specifically bisphenol A type epoxy resin with any one of the trade marks of E-55, E-51, E-44, E-42, E-35 and E-31. The curing agent is at least one selected from aliphatic diamine or polyamine, aromatic polyamine, modified aliphatic amine, organic acid, acid anhydride, modified amine curing agent DQ204H and polyamide.
Further, the method for removing the residual solvent in the system is reduced pressure distillation at 50-100 ℃ and 0.05-0.3 MPa for 60-100 min.
The preparation of the dual-effect epoxy resin additive is totally divided into two steps. The first step adopts a hydrolysis cosolvent which can be mutually soluble with a precursor tetraethyl titanate and deionized water, and can dilute and uniformly mix the tetraethyl titanate and the deionized water; in addition, the hydrolysis is inhibited, and the slow proceeding of the hydrolysis reaction is ensured, thereby obtaining the nano TiO2And (3) sol. Secondly, the nano TiO in the sol is coupled by titanate coupling agent2The particles are modified in situ and thenMixing it with organic ketone cosolvent capable of being mutually dissolved with sol and epoxy resin prepolymer to obtain modified nano TiO2Sol, i.e. a dual effect epoxy additive. TiO in the resulting additive product2The average particle size of the particles was 9.4 nm. When the dual-effect epoxy resin additive is used, the organic ketone cosolvent contained in the additive can react with the nano TiO2The hydrolysis cosolvent and the epoxy resin prepolymer in the sol are mutually soluble, so that the problem of poor compatibility of the sol and the epoxy resin prepolymer is solved, the good mixing of the sol and the epoxy resin prepolymer is ensured, and the system is clear and has no phase separation. The epoxy resin prepolymer after the solvent is removed by reduced pressure distillation is in a transparent state, and the nano TiO in the modified sol is effectively removed2The particles are dispersed in the epoxy resin prepolymer and are uniformly dispersed in a nanoscale, and finally, the high-toughness epoxy resin material can be obtained by curing and crosslinking.
Compared with the prior art, the invention has the following beneficial effects:
(1) solves the problem of nano TiO2The particles are easy to agglomerate and disperse unevenly in high-viscosity resin, and the detection shows that the modified nano TiO is2Nano TiO in sol2The average particle diameter of the particles is 9.4nm, and the particles are uniformly dispersed in an epoxy resin matrix in a nanometer scale.
(2) The method overcomes the defects of high energy consumption, time consumption and uneven dispersion of a direct nanoparticle dispersion method, various raw materials of an in-situ dispersion polymerization method, difficult control of process reaction and the like, and has the advantages of simple and independent process, easiness in operation, low equipment requirement, large-scale production and the like.
(3) The impact toughness of the cured epoxy resin is improved by about 4.5 times (108 KJ/m)2) The toughening effect is obvious, the tensile strength and the bending strength of the product are not reduced but improved, and the problem that the strength is reduced by most toughening methods is solved.
(4) Nano TiO 22The particles reduce the temperature of exothermic peak of epoxy resin curing, and the curing activation energy is reduced; with unmodified epoxy resinsCompared with the prior art, the temperature of the initial exothermic peak, the peak top and the final exothermic peak of the modified epoxy resin is reduced by about 30-40 ℃; the gelation time is shortened by nearly half under the same curing temperature, and a great deal of energy consumption can be reduced in production.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following embodiments are further described.
The raw material reagents used in the invention are all commonly sold in the market.
Tensile strength tests of samples in the examples of the invention were carried out according to GB 1040-79, flexural strength tests according to GB 1042-79, impact toughness tests according to GB 1043-79 and epoxy gel time tests according to GB 12007.7-1989. The synchronous thermal analyzer used for thermal analysis was model STA449F3/STA449F 3.
Example 1
Firstly, uniformly mixing a cosolvent 1(0.9mL of propanol), a hydrolysis catalyst (0.45mL of dilute hydrochloric acid with the mass fraction of 30%) and deionized water (0.16g) according to a proportion, then adding 0.5g of tetraethyl titanate into the mixture according to the dropping speed of 1g/min, stirring for 20min to carry out hydrolysis reaction, and obtaining the nano TiO2And (3) sol.
Then 0.01g titanate coupling agent (titanate TTS) is added into the nano TiO2Stirring the sol for 10min for in-situ modification, adding a cosolvent 2(5mL of butanone) after the modification is finished, and uniformly mixing to obtain the prepared modified nano TiO2Sol, i.e. epoxy resin additive.
Prepared modified nano TiO2Adding the sol into 80g of epoxy resin prepolymer (E-51 type epoxy resin), stirring for 1h to uniformly mix, then carrying out reduced pressure distillation for 100min at 100 ℃ and 0.05MP, removing the solvent to obtain modified epoxy resin prepolymer, finally adding 25g of amine curing agent (modified amine curing agent DQ204H) into the modified epoxy resin prepolymer, uniformly mixing, and curing for 7h at 100 ℃.
Example 2
First, co-solvent 1(1.8mL propanol), was hydrolyzed in proportionUniformly mixing a catalyst (0.9mL of dilute hydrochloric acid with the mass fraction of 30%) and deionized water (0.32g), adding 1.0g of tetraethyl titanate into the mixture at the dropping speed of 1g/min, stirring for 20min, and carrying out hydrolysis reaction to obtain the nano TiO2And (3) sol.
Then 0.02g titanate coupling agent (titanate TTS) is added into the nano TiO2Stirring the sol for 10min for in-situ modification, adding a cosolvent 2(5mL of butanone) after the modification is finished, and uniformly mixing to obtain the prepared modified nano TiO2Sol, i.e. epoxy resin additive.
Prepared modified nano TiO2Adding the sol into 80g of epoxy resin prepolymer (E-51 type epoxy resin), stirring for 1h to uniformly mix, then carrying out reduced pressure distillation for 100min at 100 ℃ and 0.05MP, removing the solvent to obtain modified epoxy resin prepolymer, finally adding 25g of amine curing agent (modified amine curing agent DQ204H) into the modified epoxy resin prepolymer, uniformly mixing, and curing for 7h at 100 ℃.
Example 3
Firstly, uniformly mixing a cosolvent 1(2.7mL of propanol), a hydrolysis catalyst (1.35mL of dilute hydrochloric acid with the mass fraction of 30%) and deionized water (0.48g) according to a proportion, then adding 1.5g of tetraethyl titanate into the mixture according to the dropping speed of 1g/min, stirring for 10min to carry out hydrolysis reaction, and obtaining the nano TiO2And (3) sol.
Then 0.03g titanate coupling agent (titanate TTS) is added into the nano TiO2Stirring the sol for 10min for in-situ modification, adding a cosolvent 2(5mL of butanone) after the modification is finished, and uniformly mixing to obtain the prepared modified nano TiO2Sol, i.e. epoxy resin additive.
Prepared modified nano TiO2Adding the sol into 80g of epoxy resin prepolymer (E-51 type epoxy resin), stirring for 1h to uniformly mix, then carrying out reduced pressure distillation for 100min at 100 ℃ and 0.05MP, removing the solvent to obtain modified epoxy resin prepolymer, finally adding 25g of amine curing agent (modified amine curing agent DQ204H) into the modified epoxy resin prepolymer, uniformly mixing, and curing for 7h at 100 ℃.
Example 4
Firstly, uniformly mixing a cosolvent 1(3.6mL of propanol), a hydrolysis catalyst (1.8mL of dilute hydrochloric acid with the mass fraction of 30%) and deionized water (0.64g) according to a proportion, then adding 2.0g of tetraethyl titanate into the mixture according to the dropping speed of 1g/min, stirring for 20min to carry out hydrolysis reaction, and obtaining the nano TiO2And (3) sol.
Then 0.04g titanate coupling agent (titanate TTS) is added into the nano TiO2Stirring the sol for 10min for in-situ modification, adding a cosolvent 2(5mL of butanone) after the modification is finished, and uniformly mixing to obtain the prepared modified nano TiO2Sol, i.e. epoxy resin additive.
Prepared modified nano TiO2Adding the sol into 80g of epoxy resin prepolymer (E-51 type epoxy resin), stirring for 1h to uniformly mix, then carrying out reduced pressure distillation for 100min at 100 ℃ and 0.05MP, removing the solvent to obtain modified epoxy resin prepolymer, finally adding 25g of amine curing agent (modified amine curing agent DQ204H) into the modified epoxy resin prepolymer, uniformly mixing, and curing for 7h at 100 ℃.
Control group
Firstly, adding a cosolvent 2(5mL of butanone) into 80g of epoxy resin prepolymer (E-51 type epoxy resin), stirring for 1h to uniformly mix, then carrying out reduced pressure distillation for 100min at 100 ℃ and 0.05MP, removing the solvent to obtain a modified epoxy resin prepolymer, finally adding 25g of amine curing agent (modified amine curing agent DQ204H) into the modified epoxy resin prepolymer, uniformly mixing, and curing for 7h at 100 ℃.
The epoxy resin products obtained in examples 1 to 4 and the control were subjected to the corresponding tests according to the above-mentioned standards, and the results are shown in Table 1.
TABLE 1 mechanical Properties of cured epoxy resin samples
As can be seen from Table 1, the impact toughness of the blank control was 19.4KJ/m2Adding a certain amount of the modified nano TiO provided by the invention2After sol, the impact toughness of the epoxy resin sample is increased all the time, and the maximum value of the impact toughness is 108KJ/m2The toughening effect is very obvious because the toughening effect is increased by 4.5 times.
Also, the tensile strength and the flexural strength of the epoxy resin products obtained in examples 1 to 4 were not decreased but increased as compared with those of the blank control, which indicates that the epoxy resin products could be reinforced while being toughened. This is because TiO2The nano particles have larger specific surface area, so that the nano particles are added into an EP matrix, active groups on the surfaces of the nano particles react with EP molecular chains under the action of a titanate coupling agent to generate a force larger than the action of van der Waals force, and thus the nano particles and the EP matrix form good interface combination. When the system is acted by external force, the nano particles transmit the force to the periphery and induce microcracks in the EP matrix (on one hand, part of energy can be absorbed, and on the other hand, the nano particles can also be used as cross-linking points of molecular chains to hinder the expansion of the microcracks), thereby achieving the aim of toughening. The addition amount of the epoxy resin additive is very small and is far lower than that required by a common physical blending method, which fully embodies the nanoscale TiO2Excellent filling property, and can greatly improve the performance of the material without using large amount.
The epoxy resin products obtained in examples 1 to 4 and the control were subjected to DTA and gelation time (100 ℃) tests in accordance with the relevant standards, and the results are shown in tables 2 to 3, respectively.
TABLE 2 DTA data sheet for cured epoxy resin samples
TABLE 3 gelation time data Table for cured epoxy resin samples at 100 deg.C
As can be seen from tables 2 and 3, the blank control samples showed exothermic peak onset, peak top and peak endThe temperatures are 117, 186 and 217 ℃, and the gelation time is 122min at 100 ℃; adding a certain amount of the modified nano TiO provided by the invention2After sol is carried out, the exothermic peak initial, peak top and peak final temperatures of curing can be reduced by 30-40 ℃ at most, and the gelation time is shortened by nearly half under the same curing temperature. This is mainly due to the nano TiO2Ti in the particles has a vacant orbital capable of forming a coordination complex with an epoxy group to perform a catalytic polymerization reaction. In addition, the autocatalytic reaction of the epoxy resin is caused by hydroxyl, and the added nano TiO2The surface has a large number of hydroxyl groups which can increase the cross-linking points of chemical reaction, so that the nano TiO2The curing reaction temperature of the epoxy resin can be reduced, and the gelation time is shortened, namely the curing reaction speed is accelerated.
Claims (7)
1. A preparation method of an epoxy resin additive with double effects of toughening and curing temperature reduction is characterized by comprising the following steps:
(a) preparation of nano TiO by sol-gel method2The sol comprises the following specific steps: putting alcohol cosolvent and hydrolysis catalyst into water to obtain a mixture, dropwise adding a titanium source into the mixture under the stirring state to obtain nano TiO2Sol;
(b) use of titanate coupling agent to nano TiO2Modifying the sol, which comprises the following steps: dripping titanate coupling agent into the nano TiO2Adding organic ketone cosolvent into the sol, and uniformly mixing to obtain the modified nano TiO2The sol is a dual-effect epoxy resin additive;
the alcohol cosolvent is at least one selected from methanol, ethanol, propanol, butanol, isopropanol and ethylene glycol, the hydrolysis catalyst is any one selected from citric acid, acetic acid and dilute hydrochloric acid, the titanium source is tetraethyl titanate, and the organic ketone cosolvent is at least one selected from acetone, methyl ethyl ketone, cyclohexanone, butanone, methyl isobutyl ketone, isophorone and diacetone alcohol.
2. The method of claim 1, wherein: the volume ratio of the alcohol cosolvent, the hydrolysis catalyst and the titanium source required by the reaction is 1-5:0.1-2:1, and the using amount of water is 1-6 times of the molar amount of the titanium source.
3. The method of claim 1, wherein: the titanate coupling agent is selected from any one of titanate TTS, pyrophosphate titanate, bis (dioctyloxypyrophosphate) ethylene titanate, tetraisopropylbis (dioctylphosphite acyloxy) titanate and isopropyltrioleoxy titanate; the dosage of the titanate coupling agent is 1 to 5 percent of the mass of the titanium source, and the dosage of the organic ketone cosolvent is 3 to 5 percent of the mass of the epoxy resin.
4. An epoxy resin additive having both toughening and curing temperature lowering effects obtainable by the process according to any one of claims 1 to 3.
5. A method of using an epoxy resin additive made according to the method of any of claims 1-3, characterized by the steps of: and (3) uniformly mixing the epoxy resin additive and the epoxy resin prepolymer, removing the residual solvent of the system to obtain a modified epoxy resin prepolymer, adding the curing agent and other auxiliaries, and uniformly mixing.
6. Use according to claim 5, characterized in that: the epoxy resin prepolymer is specifically bisphenol A type epoxy resin with the trade name of any one of E-55, E-51, E-44, E-42, E-35 and E-31; the curing agent is at least one selected from aliphatic diamine or polyamine, aromatic polyamine, modified aliphatic amine, organic acid, acid anhydride, modified amine curing agent DQ204H and polyamide.
7. Use according to claim 5, characterized in that: the method for removing the residual solvent in the system is reduced pressure distillation at 50-100 deg.C under 0.05-0.3 MPa for 60-100 min.
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