CN101712749B - Silicon nitride hybridization type epoxy resin curing agent and preparation method and application thereof - Google Patents
Silicon nitride hybridization type epoxy resin curing agent and preparation method and application thereof Download PDFInfo
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- CN101712749B CN101712749B CN2009101940193A CN200910194019A CN101712749B CN 101712749 B CN101712749 B CN 101712749B CN 2009101940193 A CN2009101940193 A CN 2009101940193A CN 200910194019 A CN200910194019 A CN 200910194019A CN 101712749 B CN101712749 B CN 101712749B
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Abstract
The invention relates to an epoxy resin curing agent, in particular to a silicon nitride hybridization type epoxy resin curing agent and a preparation method and application thereof. The curing agent has a structure shown by a formula (1), wherein R1, R2, R3, R4, R5 and R6 are hydrogen or epoxy silane groups containing amino or imino, and the R1, the R2, the R3, the R4 the R5 and the R6 cannot be hydrogen at the same time. The preparation method for the curing agent comprises the following steps of: performing hydroxymethylation reaction of melamine and solution of formaldehyde; then adding epoxy silane containing amino or imino into the mixture; and adjusting the temperature to between 70 and 130 DEG C, and performing reaction for 0.5 to 5 hours to obtain a needed product. The curing agent is mainly used for curing epoxy resin and simultaneously can improve the fire resistance and the mechanical properties of the epoxy resin.
Description
Technical field
The present invention relates to epoxy curing agent, be specifically related to a kind of silicon nitride hybridization type epoxy resin solidifying agent and its production and application.
Technical background
Resins, epoxy has good cohesiveness, physical strength and electrical insulating property etc., but the cured article of pure Resins, epoxy exists shortcomings such as fragility, fatiguability, thermotolerance and flame retardant resistance deficiency greatly to limit the application of Resins, epoxy.It is epoxy resin toughened that the research of epoxy resin roughening mainly contains rubber elastomer at present, polymer toughening epoxy resin with nucleocapsid structure, rigidity nano-particle toughening epoxy-resin systems, thermoplastic resin is epoxy resin toughened, passes the network structure modified epoxy mutually.Rubber-toughened epoxy resin can reach toughness reinforcing preferably purpose, but the consistency between rubber and the Resins, epoxy is very poor, and the adding of flexible rubber segmental makes the second-order transition temperature of Resins, epoxy reduce, the existence of unsaturated link(age) in the rubber simultaneously is easy to the oxidized very big influence that makes that modified effect is received.Problems such as the polymer toughening epoxy resin with nucleocapsid structure can solve the compatibility problem between rubber and the Resins, epoxy, but still has easy oxidation, and thermotolerance is low.The rigidity nanoparticle can be epoxy resin toughened, but because the specific surface area of nanoparticle is big, the surfactivity height, reunite easily and the matching of every physicochemical property and matrix bad and limited its application.Thermoplastic resin inierpeneirating network structure epoxy resin toughened and formation Resins, epoxy also can reach toughness reinforcing purpose, but with identical with upper type, makes the flame retardant resistance of Resins, epoxy reduce owing to introduced organic structure in toughness reinforcing.
Above-mentioned epoxy resin toughened method all is to lean against in the Resins, epoxy to add the third material and realize, and can not in toughness reinforcing the flame retardant resistance of Resins, epoxy is improved.Hybrid material is a kind of type material that development in recent years is got up, and it has better physical mechanical property, excellent comprehensive performances such as good heat-resistant and flame retardant resistance.The performance of utilizing hybrid material to improve Resins, epoxy has at home and abroad obtained paying close attention to widely at present.But this tend to exist and Resins, epoxy between the problem of consistency.
Summary of the invention
The purpose of invention is to overcome the above-mentioned shortcoming and defect that exists in the prior art, directly provides a kind of toughening effect good, the silicon nitride hybridization type epoxy resin curing agent with rigidity and flame retardant resistance.
Another object of the present invention is to provide the preparation method of above-mentioned epoxy curing agent.
A further object of the present invention provides the concrete application of above-mentioned solidifying agent in epoxy resin cure.
In order to realize above purpose, the invention provides following technical scheme:
A kind of silicon nitride hybridization type epoxy resin curing agent, it has general structure as the formula (1):
(1)
Wherein, R
1, R
2, R
3, R
4, R
5, R
6For hydrogen or
And, R
1, R
2, R
3, R
4, R
5, R
6Can not be hydrogen simultaneously;
The structure of X is:
Wherein, R " be hydrogen, alkyl, aryl or arylidene; R ' is the alkyl link, contains the alkyl of direct-connected or side chain of 1-18 carbon of the alkyl of direct-connected or side chain of 1-18 carbon of Sauerstoffatom or nitrogen atom;
A
1Be C
1～4Saturated alkyl, A
2Be C
1～4Saturated alkyl.
The present invention also provides a kind of preparation method of described silicon nitride hybridization type epoxy resin curing agent, may further comprise the steps:
Count by weight, at first, with 100 parts trimeric cyanamide, 100-400 part massfraction is the formaldehyde solution of 20%-37%, regulates pH value to 7-10, under 50-90 ℃, and hydroxymethylation 20-90 minute; And then will contain organoalkoxysilane 300-1500 part of amino or imino-, and adjust the temperature to 70-130 ℃, react and can obtain needed product after 0.5-5 hour.
The organoalkoxysilane that contains amino or imino-has structure as the formula (2):
(2)
Wherein, R " be hydrogen, alkyl, aryl or arylidene;
R ' is the alkyl link, contains the alkyl of direct-connected or side chain of 1-18 carbon of the alkyl of direct-connected or side chain of 1-18 carbon of Sauerstoffatom or nitrogen atom;
M
1Be hydrogen, methyl, ethyl, n-propyl, sec.-propyl or butyl;
M
2Be hydrogen, methyl, ethyl, n-propyl, sec.-propyl or butyl;
N is 0,1 or 2.
In the aforesaid method, as preferably, described catalyzer is a triphenyl phosphorus, triethylamine, dibutyl tin dilaurate, aluminum chloride etc.
As preferably, described catalyst consumption is the 0.05%-5% of reaction system material gross weight, more preferably 0.5%-1%.
The present invention also provides the application of above-mentioned silicon nitride hybridization type epoxy resin curing agent, is mainly used in the curing of Resins, epoxy, and preferably is used for a kind of solidification process, promptly be adopt single with or with the form of other solidifying agent coupling; Described other solidifying agent comprises aromatic polyamine class solidifying agent, dicyandiamide class solidifying agent, resol class solidifying agent or two or more mixture in them.
In above-mentioned application, as preferably, described amine curing agent is 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfone, O-Phenylene Diamine, mphenylenediamine or divinyl tetramine;
Described dicyandiamide class solidifying agent is a dicyandiamide;
Described phenolic solidifying agent is linear phenol type resol or linear o-cresol formaldehyde resin.
Described Resins, epoxy is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol A-type novolac epoxy, the one or more kinds of mixtures in the ortho-cresol formaldehyde Resins, epoxy.
More preferably, the oxirane value of bisphenol A type epoxy resin is 0.10-0.56mol/100g, the oxirane value of bisphenol f type epoxy resin is 0.40-0.80mol/100g, and the oxirane value of bisphenol A-type novolac epoxy is 0.30-0.60mol/100g, and the oxirane value of novolac epoxy is 0.3-0.5mol/100g.
Solidifying agent provided by the invention is the organic inorganic hybridization thing of nanoscale, middle kernel organic group is an inflexible trimeric cyanamide group, the periphery is to contain amino or imino-silane coupling agent, can be separately or mix with other solidifying agent and to use the mixture that solidifies a kind of or two or more Resins, epoxy.It is compared with existing solidifying agent, has following advantage:
(1) toughness through solidifying agent solidified Resins, epoxy of the present invention significantly improves, and its shock strength reaches 10.8-25.6kJ/m
2
(2) flame retardant resistance through solidifying agent solidified Resins, epoxy of the present invention is greatly enhanced, and flame retardant resistance is represented with limiting oxygen index(LOI), can reach 20-39, more than the corresponding limiting oxygen index(LOI) height of pure epoxy resin.
Specific embodiment
Below in conjunction with embodiment, the present invention is done detailed description further, but implementation of the present invention is not limited thereto.
Embodiment 1
With the 100g trimeric cyanamide, the formaldehyde solution of 100g37%, regulate PH=8, reacted 50 minutes down at 80 ℃, add the 200g TSL 8330 then, the dibutyl tin dilaurate catalyzer that adds 1.5g reacted 0.5 hour down at 130 ℃, both can obtain containing the solidifying agent of nitrogen silicon hybrid.
FT-IR (500-4000cm
-1): 3359cm
-1(OH ,-NH2), 2940cm
-1, 2834cm
-1(C-H), 2360
-1(C=N-), 1565cm
-1(
Ring absorbs), 1259,1199cm-1 (Si-O-Si), 1027,1106cm-1 is (C-O-C)
Because the amount difference that each reaction is adding causes the structure difference of institute's synthetic nitrogenated silicon hydridization type solidifying agent, and the infrared spectra structure shows that the variation of main functional group is similar substantially.
Embodiment 2, and embodiment 3, and embodiment 4, and embodiment 5, and the spectral composition of embodiment 6 is substantially the same manner as Example 1, data that can reference example 1.
The resulting molecular weight of Theoretical Calculation is simultaneously: 365.7g/mol, and the actual molecular weight of being measured is: 376.4g/mol. actual value and theoretical value basically identical.
With 100g bisphenol A epoxide resin (oxirane value is 0.51mol/100g), 45.92g be cured after the solidifying agent of nitrogenated silicon hybrid and 12.57g diaminodiphenyl-methane at room temperature mix, silicone content is 2.52% in the cured article, and nitrogen content is 2.35%, and shock strength reaches 23.86kJ/m
2, flame retardant resistance reaches 28.4
Embodiment 2
With the 100g trimeric cyanamide, the formaldehyde solution of 100g37%, regulate PH=8, reacted 50 minutes down at 80 ℃, add the amino butyl triethoxyl silane of 250g then, the dibutyl tin dilaurate catalyzer that adds 1.0g reacted 0.5 hour down at 120 ℃, both can obtain nitrogenated silicon hydridization type solidifying agent.
The resulting molecular weight of Theoretical Calculation is simultaneously: 375.4g/mol, and the actual molecular weight of being measured is: 382.9g/mol. actual value and theoretical value basically identical.
With 100g bisphenol A epoxide resin (oxirane value is 0.54mol/100g), 34.44g be cured after the solidifying agent of nitrogenated silicon hybrid and 18.58g diaminodiphenyl-methane at room temperature mix, silicon content is 1.54% in the cured article, and nitrogen content is 2.47%, and shock strength reaches 24.25kJ/m
2, flame retardant resistance reaches 37.0.
Embodiment 3
With the 100g trimeric cyanamide, the formaldehyde solution of 100g37% is regulated PH=9, reacted 50 minutes down at 75 ℃, add the amino butyl triethoxyl silane of 250g then, add the triphenyl phosphorus catalyzer of 1.5g, reacted 2 hours down at 100 ℃, both can obtain the solidifying agent of nitrogenated silicon hydridization type.
The resulting molecule of Theoretical Calculation heavily is simultaneously: 375.4g/mol, and the actual molecular weight of being measured is: 384.6g/mol. actual value and theoretical value basically identical.
With 50g bisphenol A epoxide resin (oxirane value is 0.51mol/100g) and 50g bisphenol A-type novolac epoxy (oxirane value is 0.51mol/100g), 108.37g the solidifying agent of nitrogenated silicon hybrid is cured, silicon content is 3.55% in the cured article, nitrogen content is 1.71%, and shock strength reaches 17.92kJ/m
2, flame retardant resistance reaches 36.2.
Embodiment 4
With the 100g trimeric cyanamide, the formaldehyde solution of 150g37% is regulated PH=10,60 ℃ were reacted 70 minutes down, added 200g methylamino propyl trimethoxy silicane then, added the triethylamine catalyzer of 1.5g, reacted 2.5 hours down at 100 ℃, both can obtain nitrogenated silicon hybrid type solidifying agent.
The resulting molecular weight of Theoretical Calculation is simultaneously: 393.2g/mol, and the actual molecular weight of being measured is: 398.1g/mol. actual value and theoretical value basically identical.
With 100g bisphenol A epoxide resin (oxirane value is 0.44mol/100g), 85.46g be cured after the solidifying agent of nitrogenated silicon hybrid and 23.13g resol at room temperature mix, silicon content is 6.12% in the cured article, and nitrogen content is 2.96%, and shock strength reaches 24.35kJ/m
2, flame retardant resistance reaches 37.8.
Embodiment 5
With the 100g trimeric cyanamide, the formaldehyde solution of 180g37%, regulate PH=8, reacted 50 minutes down at 80 ℃, add the 200g TSL 8330 then, the dibutyl tin dilaurate catalyzer that adds 1.2g reacted 3 hours down at 100 ℃, both can obtain the solidifying agent of nitrogenated silicon hydridization type.
The resulting molecular weight of Theoretical Calculation is simultaneously: 319.9g/mol, and the actual molecular weight of being measured is: 331.3g/mol. actual value and theoretical value basically identical.
With the composite epoxy resin of 80g bisphenol F epoxy resin (oxirane value is 0.51mol/100g) with 20g bisphenol A epoxide resin (oxirane value is 0.44mol/100g), 15.86g be cured after the solidifying agent of nitrogenated silicon hybrid and 25.10g diamino diphenyl sulfone at room temperature mix, silicon content 0.76% in the cured article, nitrogen content is 2.39%, and shock strength reaches 14.52kJ/m
2, flame retardant resistance reaches 22.7.
Embodiment 6
With the 100g trimeric cyanamide, the formaldehyde solution of 100g37% is regulated PH=8, reacted 50 minutes down at 80 ℃, add the 200g TSL 8330 then, add the triphenyl phosphorus catalyzer of 1.5g, reacted 4 hours down at 80 ℃, both can obtain containing the solidifying agent of silicon nitride hybridization type.
The resulting molecular weight of Theoretical Calculation is simultaneously: 365.7g/mol, and the actual molecular weight of being measured is: 372.3g/mol. actual value and theoretical value basically identical.
With the composite epoxy resin of 50g bisphenol-A phenolic Resins, epoxy (oxirane value is 0.51mol/100g) with bisphenol A type epoxy resin (oxirane value is 0.51mol/100g), 45.92g be cured after the solidifying agent of nitrogenated silicon hybrid and 42.62g resol at room temperature mix, silicone content is 1.96% in the cured article, nitrogen content is 0.95%, and shock strength reaches 24.01kJ/m
2, flame retardant resistance reaches 27.9.
The comparative example 1
(oxirane value: 0.51mol/100g) resulting condensate performance is as shown in table 1 for the compound after fixing bisphenol A type epoxy resin of silicon nitride hybridization type epoxy hardener that the present invention is prepared and ordinary epoxy resin solidifying agent.
Wherein, nitrogenated silicon hydridization type solidifying agent is represented with A in table 1, its preparation method is as follows: with the 100g trimeric cyanamide, the formaldehyde solution of 100g 37% is regulated PH=9, reacts 50 minutes down at 80 ℃, add the 200g TSL 8330 then, the dibutyl tin dilaurate catalyzer that adds 1.5g reacted 0.5 hour down at 130 ℃, both can obtain containing the solidifying agent of nitrogen silicon hybrid.The resulting molecular weight of Theoretical Calculation is: 365.7g/mol, and the actual value of being measured is 370.5g/mol. actual value and theoretical value basically identical.
Used common epoxy curing agent is that 4,4 ' diaminodiphenyl-methane (DDM), the total amount of solidifying agent is calculated according to the mol ratio of epoxy group(ing) and amino hydrogen at 1: 1.
The result shows: the flame retardant properties that silicon phospha type solidifying agent and amine curing agent solidify the formed cured article of bisphenol A type epoxy resin jointly raises along with the rising of the ratio of silicon phospha type solidifying agent in the solidifying agent, shock strength is then along with the increase of silicon phospha type curing agent content presents appearance increase back downward trend, in scope of experiment, when the amount of silicon phospha type solidifying agent was 55.10, the shock strength maximum reached 24.57kJm
-2
Table 1 silicon nitride hybridization type solidifying agent and DDM solidify the performance of E-51 gained cured article
The comparative example 2
The prepared silicon nitride hybridization type epoxy resin of the present invention can not only mix with amine curing agent to make with solidifying agent and is used for solidifying bisphenol A type epoxy resin, and can make the Resins, epoxy that is used for solidifying other with the resol mixing, provide prepared silicon nitride hybridization type solidifying agent and the resol (hydroxyl equivalent is 105g/100mol) of the present invention as table 2 and formed the performance index that compound solidifying agent is cured bisphenol A-type resol (oxirane value is 0.44mol/100g).
Wherein, the silicon nitride hybridization type solidifying agent represents with B that in table 2 its preparation method is as follows.Formaldehyde solution with 100g trimeric cyanamide and 195g37%, regulate about PH=9, adding catalyzer triphenyl phosphorus 2g and anilinomethyl triethoxysilane 647g reacted 2 hours down at 90 ℃ after reacting 30 minutes under 75 ℃, can obtain needed silicon nitride hybridization type solidifying agent.
The resulting molecular weight of Theoretical Calculation is: 778.1g/mol, and the actual value of being measured is 780.5g/mol. actual value and theoretical value basically identical.
Compound the making of this then silicon nitride hybridization type solidifying agent and resol is used for solidifying bisphenol-A phenolic Resins, epoxy.The consumption of solidifying agent is according to active hydrogen 1: 1 resulting consumption of calculating of ratio row with epoxy group(ing).
The result shows: the flame retardant properties that silicon phospha type solidifying agent and phenolic resin curative solidify the formed cured article of bisphenol A type epoxy resin jointly raises along with the rising of the ratio of silicon phospha type solidifying agent in the solidifying agent, shock strength is then along with the increase of silicon phospha type curing agent content presents appearance increase back downward trend, in scope of experiment, when the amount of silicon phospha type solidifying agent was 99.17, the shock strength maximum reached 25.56kJm
-2
Table 2 nitrogen silicon hybrid and phenolic resin curing bisphenol A-type phenolic resin curing rerum natura can indexs
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. silicon nitride hybridization type epoxy resin curing agent, it is characterized in that: it has general structure as the formula (1):
(1)
Wherein, R
1, R
2, R
3, R
4, R
5, R
6For
Or hydrogen, and, R
1, R
2, R
3, R
4, R
5, R
6Can not be hydrogen simultaneously;
The structure of X is:
Wherein, R " be hydrogen, alkyl or aryl; R ' is for containing the C of Sauerstoffatom
1～18The alkylene of straight chain or side chain or the C of nitrogen atom
1～18The alkylene of straight chain or side chain;
A
1Be C
1～4Saturated alkyl, A
2Be C
1～4Saturated alkyl.
2. the preparation method of a silicon nitride hybridization type epoxy resin curing agent according to claim 1 is characterized in that may further comprise the steps:
Count by weight, at first, with 100 parts trimeric cyanamide, 100-400 part massfraction is the formaldehyde solution of 20%-37%, regulates the pH value to 7-10, under 50-90 ℃, and hydroxymethylation 20-90 minute; And then add the organoalkoxysilane 300-1500 part contain amino or imino-, and adjust the temperature to 70-130 ℃, react and promptly obtain needed product after 0.5-5 hour;
The described organoalkoxysilane that contains amino or imino-is any or the two or more mixture that has in the compound of structure as the formula (2):
Wherein, R " be hydrogen, alkyl or aryl;
R ' is for containing the C of Sauerstoffatom
1～18The alkylene of straight chain or side chain or the C of nitrogen atom
1～18The alkylene of straight chain or side chain;
M
1Be hydrogen, methyl, ethyl, n-propyl, sec.-propyl or butyl;
M
2Be hydrogen, methyl, ethyl, n-propyl, sec.-propyl or butyl; N is 0.
3. the application of the described silicon nitride hybridization type epoxy resin curing agent of claim 1 is characterized in that: be used for the curing of Resins, epoxy.
4. the application of silicon nitride hybridization type epoxy resin curing agent according to claim 3 is characterized in that: described curing be adopt single with or with the form of other solidifying agent coupling; Described other solidifying agent comprises aromatic polyamine class solidifying agent, dicyandiamide class solidifying agent, resol class solidifying agent or two or more mixture in them.
5. the application of silicon nitride hybridization type epoxy resin curing agent according to claim 4 is characterized in that:
Described aromatic polyamine class solidifying agent is 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfone, O-Phenylene Diamine or mphenylenediamine;
Described dicyandiamide class solidifying agent is a dicyandiamide;
Described resol class solidifying agent is linear phenol type resol.
6. according to the application of each described silicon nitride hybridization type epoxy resin curing agent among the claim 3-5, it is characterized in that: described Resins, epoxy is bisphenol A type epoxy resin, bisphenol f type epoxy resin, the bisphenol A-type novolac epoxy, the one or more kinds of mixtures in the ortho-cresol formaldehyde Resins, epoxy.
7. the application of silicon nitride hybridization type epoxy resin curing agent according to claim 6, it is characterized in that: the oxirane value of described bisphenol A type epoxy resin is 0.10-0.56mol/100g, the oxirane value of bisphenol f type epoxy resin is 0.40-0.80mol/100g, the oxirane value of bisphenol A-type novolac epoxy is 0.30-0.60mol/100g, and the oxirane value of ortho-cresol formaldehyde Resins, epoxy is 0.3-0.5mol/100g.
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