CN101701058B - Epoxy resin containing melamine-organic silicon hybrid structure and preparation method and application thereof - Google Patents
Epoxy resin containing melamine-organic silicon hybrid structure and preparation method and application thereof Download PDFInfo
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- CN101701058B CN101701058B CN2009101940206A CN200910194020A CN101701058B CN 101701058 B CN101701058 B CN 101701058B CN 2009101940206 A CN2009101940206 A CN 2009101940206A CN 200910194020 A CN200910194020 A CN 200910194020A CN 101701058 B CN101701058 B CN 101701058B
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Abstract
The invention relates to an epoxy resin, in particular to the epoxy resin containing a melamine-organic silicon hybrid structure and a preparation method and an application thereof, the epoxy resin has the structure as shown in the formula (1), wherein R1, R2, R3, R4, R5 and R6 are hydrogen or epoxy silane group respectively, and R1, R2, R3, R4, R5 and R6 can not be hydrogen simultaneously. The prepration method of the epoxy resin comprises the steps of leading melamine and formaldehyde solution to react under the condition that pH is equal to 7-10, then adding a catalyst and epoxy silane, and carrying out hydrolytic condensation reaction. A cured substance of the epoxy resin or the cured substance after being compounded with other epoxy resins has excellent flame retardance and mechanical properties.
Description
Technical field
The present invention relates to Resins, epoxy, relate to a kind of Resins, epoxy that contains melamine-organic silicon hybrid structure and its production and application.
Technical background
Resins, epoxy has excellent mechanical property because of it, adhesive property, and electric property, stability and cure shrinkage are low etc., are widely used in building, coating, fields such as sizing agent and electronic apparatus material.Yet there is fragility in the cured article of ordinary epoxy resin, fatiguability, and shortcomings such as thermotolerance, flame retardant resistance deficiency, for example the limiting oxygen index(LOI) of ordinary epoxy resin only is 19.8, belongs to inflammable material, makes Resins, epoxy exist potential safety hazard when using.Therefore, how to improve Resins, epoxy flame retardant properties, make it to better meet increasingly extensive Application Areas, become the focus of domestic and international research.
At present, using maximum fire-retardant epoxy resins on the market is Resins, epoxy such as the tetrabromo bisphenol-a epoxy resin that contains halogen, but can produce many bromines diphenylene-oxide and many bromos dibenzodioxin alkane etc. in this based epoxy resin combustion processes to the virulent material of human body.Therefore, the Resins, epoxy of research halogen-free flame-retardant becomes the focus of present research.The method that improves ethoxyline resin antiflaming mainly contains additive process and reaction method two classes.Additive process promptly adds halogen-free flame retardants in Resins, epoxy makes the cured article of Resins, epoxy reach the purpose of flame retardant resistance, but the fire retardant that additive process added in use is easy to migration to come out, and can make that still there is potential safety hazard in the use of Resins, epoxy.The Halogenless fire retarded epoxy resin of response type is the group of flame retardant resistance to be incorporated into the flame retardant resistance structure by the method with Resins, epoxy or epoxy curing agent reaction in the cross-linked network of Resins, epoxy go, problems such as potential safety hazard when the Resins, epoxy that the halogen-free fire-retardant epoxy resin that this method resultant Resins, epoxy has overcome the additive process preparation in use brings because of the passage of additive uses, can reach good flame-retardant effect, and have fabulous thermostability and carbon forming rate.So the Resins, epoxy that the Resins, epoxy that utilizes this environmental protection flame retardant replaces containing halogen fire retardant has very significant meaning.
In recent years, the research about the Resins, epoxy of environmental protection flame retardant mainly concentrates on organosilicon organophosphorus modified epoxy field.According to the principle of macromolecular structure and property relationship, the Resins, epoxy of this class organosilicon or organophosphorus modification has flame retardant effect preferably with respect to ordinary epoxy resin, but tends to make the thermal characteristics and the mechanical properties decrease of Resins, epoxy.
Summary of the invention:
Technical problem at above-mentioned prior art exists the purpose of this invention is to provide a kind of Resins, epoxy that contains melamine-organic silicon hybrid structure, has flame retardant resistance preferably, thermotolerance and mechanical property.
Another object of the present invention provides the preparation method of above-mentioned melamine-organic silicon hybrid thing Resins, epoxy.This Resins, epoxy be trimeric cyanamide behind the formaldehyde methylolation, carry out with material after the hydrolysis of silicoorganic compound that reaction in obtains.
A further object of the present invention provides the concrete application mode of above-mentioned Resins, epoxy.
In order to reach above purpose, the invention provides following technical scheme:
A kind of Resins, epoxy that contains melamine-organic silicon hybrid structure, it has general structure as the formula (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; R is the C that contains epoxy group(ing)
1-10Alkyl.
The present invention also provides a kind of preparation method who contains the Resins, epoxy of melamine-organic silicon hybrid structure, comprises the steps:
According to the weight part meter, with the massfraction of 100 parts trimeric cyanamides and 64.35-390 part be the formaldehyde solution of 20%-37% under the PH=7-10 condition in 60-90 ℃ of reaction 20-80 minute, add then catalyzer and 150-1200 part epoxy radicals silicone hydride 60-100 ℃ of following hydrolysis-condensation reaction 1-5 hour as preferred, the structure of used epoxy radicals silicone hydride as the formula (2):
In the formula (2), R ' is the straight chain or the side chain alkyl link of 3～18 carbon;
R
1Be methyl, ethyl, n-propyl, sec.-propyl or butyl;
R
2Be methyl, ethyl, n-propyl, sec.-propyl or butyl;
N is 0 or 1.
As preferably, described catalyzer comprises dibutyl tin dilaurate, triethylamine, triphenyl phosphorus, aluminum chloride, zinc dichloride or iron trichloride.
As preferably, described catalyst consumption is for being the 0.05%-1% of reaction system material gross weight, more preferably 0.1-0.5%.
The present invention also provides the above-mentioned application that contains the Resins, epoxy of melamine-organic silicon hybrid structure, can be to mix use separately or with other Resins, epoxy; Described other Resins, epoxy comprise bisphenol A type epoxy resin, bisphenol f type epoxy resin, any one or two kinds of above mixtures in bisphenol A-type novolac epoxy and the novolac epoxy.
In the above-mentioned application, as preferably, 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 novolac epoxy is 0.3-0.5mol/100g.
As preferably, add high-temperature curing agent during use; Described high-temperature curing agent comprises amine curing agent, any one in Dyhard RU 100 class and the resol or two or more mixtures;
More preferably, described amine curing agent is a mphenylenediamine, Ursol D, m-xylene diamine, 4,4 ' diaminodiphenyl-methane or 4,4 ' diamino two stupid sulfones;
Described Dyhard RU 100 class solidifying agent is dicyandiamide or cyanoguanidine derivative;
Described phenolic resin curative is linear o-cresol formaldehyde resin or resol, and hydroxyl equivalent is 90-160.
Resins, epoxy provided by the invention is the hybrid of nanoscale, the trimeric cyanamide group that middle kernel organic group is the rigidity flame retardant resistance, and the periphery is the silane coupling agent that contains epoxy group(ing).Number-average molecular weight can be used as the Resins, epoxy of heat-resisting flame-retardant, perhaps with the compound use of general Resins, epoxy between 500-10000.The present invention compares with original technology has following advantage:
(1) the limiting oxygen index(LOI) LOI of the cured article of Resins, epoxy of the present invention is between 19.8-40, and shock strength is at 10.8-28kJ/m
2Limiting oxygen index(LOI) 19.8 and shock strength 10.8kJ/m with the pure epoxy resin cured article
2Comparing tool improves a lot.
(2) during the compound use of Resins, epoxy of the present invention and other Resins, epoxy, can improve the flame retardant resistance and the toughness of Resins, epoxy simultaneously.
Specific embodiment
In order to further specify the present invention, now provide some embodiments of the invention, but protection of the present invention is not limited to embodiment.
Embodiment 1
The formaldehyde solution 193.5g of 100g trimeric cyanamide and 37% is joined in the reaction flask, regulate PH=8,65 ℃ of following stirring reactions 25 minutes, add 0.293g dibutyl tin dilaurate catalyzer then, under the elevated temperature to 80 ℃, add γ-glycidoxy Trimethoxy silane 375g, stir reaction down 1.5 hours, obtain the needed melamine-organic silicon hybrid structure Resins, epoxy that contains.
Its chemical structural formula is:
Ir data is as follows:
FT-IR (500-4000cm
-1): 3365cm
-1(OH ,-NH2), 2935cm
-11 (C-H), 2385
-1(C=N-), 1578cm
-1(
Ring absorbs), 1235,1182cm-1 (Si-O-Si), 1085,1032cm-1 (C-O-C).
The oxirane value that contains the Resins, epoxy of melamine-organic silicon hybrid structure according to molecular formula calculating gained is 0.377mol/100g, and the actual numerical value that records is 0.375mol/100g, and is consistent with theoretical value.
Prepared contain melamine-organic silicon hybrid structure 30g and bisphenol A epoxide resin (oxirane value: 0.51mol/100g) 70g joins in the beaker above-mentioned, at 30 ℃ of Resins, epoxy that obtain containing melamine-organic silicon hybrid structure after down compound, ' diaminodiphenyl-methane 21.09g is cured this then used for epoxy resin 4,4 that contains melamine-organic silicon hybrid structure.The shock strength of gained cured article is 13.52kJ/m
2, LOI is 32.7.
Embodiment 2
The formaldehyde solution 257.4g of 100g trimeric cyanamide and 37% is joined in the reaction flask, regulate PH=7.5,70 ℃ of following stirring reactions 25 minutes, add 0.293g dibutyl tin dilaurate catalyzer then, under the elevated temperature to 75 ℃, add γ-glycidoxy Trimethoxy silane 375g, stir reaction down 1 hour, obtain the needed melamine-organic silicon hybrid structure Resins, epoxy that contains.Its chemical structural formula is:
The employed principle of Resins, epoxy of melamine-organic silicon hybrid structure is identical because preparation contains, so present embodiment and embodiment 3, embodiment 4, and embodiment 5, and embodiment 6, and the related data that embodiment 7 can reference example 1 no longer provides spectral data.
Calculating the oxirane value that gained contains the Resins, epoxy of melamine-organic silicon hybrid structure according to molecular formula among the embodiment 2 is 0.377mol/100g, and the actual numerical value that records is 0.36mol/100g, with the theoretical value basically identical.
Prepared contain melamine-organic silicon hybrid structure Resins, epoxy 20g and bisphenol A epoxide resin (oxirane value: 0.54mol/100g) 80g joins in the beaker above-mentioned, at 80 ℃ of mixtures that obtain containing melamine-organic silicon hybrid structure Resins, epoxy and bisphenol A epoxide resin after down compound, ' diaminodiphenyl-methane 23.36g is cured this then used for epoxy resin 4,4 that contains melamine-organic silicon hybrid structure.The shock strength of gained cured article is 16.03kJ/m
2, LOI is 28.0.
Embodiment 3
The formaldehyde solution 193.5g of 100g trimeric cyanamide and 37% is joined in the reaction flask, regulate PH=8,60 ℃ of following stirring reactions 25 minutes, add 0.290g triethylamine catalyzer then, under the elevated temperature to 85 ℃, add γ-glycidoxy triethoxyl silane 441.3g, stir reaction down 1.5 hours, obtain the needed melamine-organic silicon hybrid structure Resins, epoxy that contains.Its chemical structural formula is:
The oxirane value that contains the Resins, epoxy of melamine-organic silicon hybrid structure according to molecular formula calculating gained is 0.377mol/100g, and the actual numerical value that records is 0.374mol/100g, with the theoretical value basically identical.
Prepared contain melamine-organic silicon hybrid structure Resins, epoxy 40g and bisphenol-A phenolic Resins, epoxy (oxirane value: 0.45mol/100g) 60g joins in the beaker above-mentioned, at 30 ℃ of mixtures that obtain containing melamine-organic silicon hybrid structure Resins, epoxy and bisphenol-A phenolic Resins, epoxy after down compound, thisly then contain melamine-organic silicon hybrid structure Resins, epoxy and bisphenol-A phenolic epoxy resin composite ' diaminodiphenylsulfone(DDS) 19.99g is cured with 4,4.The shock strength of gained cured article is 21.46kJ/m
2, LOI is 36.5.
Embodiment 4
The formaldehyde solution 387g of 100g trimeric cyanamide and 37% is joined in the reaction flask, regulate PH=8,75 ℃ of following stirring reactions 60 minutes, add 0.293g dibutyl tin dilaurate catalyzer then, under the elevated temperature to 80 ℃, add γ-glycidoxy Trimethoxy silane 1125g, stir reaction down 1.5 hours, obtain the needed melamine-organic silicon hybrid structure Resins, epoxy that contains.Its chemical structural formula is:
R wherein
1Structure:
Calculating the resulting oxirane value that contains melamine-organic silicon hybrid structure Resins, epoxy according to molecular formula is 0.410mol/100g, and the oxirane value of practical measurement is 0.409mol/100g, actual value and theoretical value basically identical.
Prepared contain melamine-organic silicon hybrid structure Resins, epoxy 10g and bisphenol A epoxide resin (oxirane value: 0.51mol/100g) (oxirane value: 0.50mol/100g) 20g joins in the beaker for 70g and bisphenol-A phenolic Resins, epoxy above-mentioned, after compound under 35 ℃, obtain containing the melamine-organic silicon hybrid structure epoxy resin composite, thisly then contain the melamine-organic silicon hybrid structure epoxy resin composite ' diaminodiphenyl-methane 23.94g is cured with 4,4.The shock strength of gained cured article is 19.6kJ/m
2, LOI is 25.2.
Embodiment 5
The formaldehyde solution 193.5g of 100g trimeric cyanamide and 37% is joined in the reaction flask, regulate PH=8,65 ℃ of following stirring reactions 25 minutes, add 0.293g dibutyl tin dilaurate catalyzer then, under the elevated temperature to 80 ℃, add γ-epoxy butoxy Trimethoxy silane 318g, stir reaction down 2 hours, promptly obtain the needed melamine-organic silicon hybrid structure Resins, epoxy that contains.Its chemical structural formula is:
Calculating the resulting oxirane value that contains the Resins, epoxy of melamine-organic silicon hybrid structure according to chemical formula is: 0.358mol/100g, the practical measurement value is: 0.355mol/100g, actual value and theoretical value basically identical.
With above-mentioned prepared contain melamine-organic silicon hybrid structure Resins, epoxy 20g and bisphenol A epoxide resin (oxirane value: 0.44mol/100g) 20g and bisphenol-A phenolic Resins, epoxy (oxirane value: 0.51mol/100g) 60g with join in the beaker, after compound under 60 ℃, obtain containing the melamine-organic silicon hybrid structure epoxy resin composite, thisly then contain the melamine-organic silicon hybrid structure epoxy resin composite ' (hydroxyl equivalent: 105g/mol) 41.38g is cured for diaminodiphenyl-methane 2.03g and resol with 4,4.The shock strength of gained cured article is 15.82kJ/m
2, LOI is 30.2.
Embodiment 6
The formaldehyde solution 193.5g of 100g trimeric cyanamide and 37% is joined in the reaction flask, regulate PH=8,85 ℃ of following stirring reactions 25 minutes, add 0.293g dibutyl tin dilaurate catalyzer then, under the elevated temperature to 90 ℃, add γ-epoxy butoxymethyl diethoxy silane 623.81g, stir reaction down 1 hour, promptly obtain the needed melamine-organic silicon hybrid structure Resins, epoxy that contains.Its chemical structural formula is:
Calculating the resulting oxirane value that contains the Resins, epoxy of melamine-organic silicon hybrid structure according to chemical formula is: 0.361mol/100g, the practical measurement value is: 0.359mol/100g, actual value and theoretical value basically identical.
Prepared contain melamine-organic silicon hybrid structure Resins, epoxy 50g and bisphenol A epoxide resin (oxirane value: 0.51mol/100g) (oxirane value: 0.36mol/100g) 20g joins in the beaker for 30g and bisphenol A-type novolac epoxy above-mentioned, after compound under 50 ℃, obtain containing the melamine-organic silicon hybrid structure epoxy resin composite, thisly then contain the melamine-organic silicon hybrid structure epoxy resin composite ' (hydroxyl equivalent: 100g/mol) 22.50g is cured for diaminodiphenyl-methane 6.45g and resol with 4,4.The shock strength of gained cured article is 26.83kJ/m
2, LOI is 38.2.
Embodiment 7
The formaldehyde solution 193.5g of 100g trimeric cyanamide and 37% is joined in the reaction flask, regulate PH=8,65 ℃ of following stirring reactions 25 minutes, add the 0.293g aluminum trichloride catalyst then, under the elevated temperature to 80 ℃, add γ-glycidoxy Trimethoxy silane 375g, stir reaction down 1.5 hours, promptly obtain the needed melamine-organic silicon hybrid structure that contains.Its chemical structural formula is:
The oxirane value that contains the Resins, epoxy of melamine-organic silicon hybrid structure according to molecular formula calculating gained is 0.377mol/100g, and the actual numerical value that records is 0.374mol/100g, and is consistent with theoretical value.
Prepared contain melamine-organic silicon hybrid structure 30g and bisphenol F epoxy resin (oxirane value: 0.51mol/100g) 70g joins in the beaker above-mentioned, obtain containing the melamine-organic silicon hybrid structure epoxy resin composite at 30 ℃ after down compound, thisly then contain the melamine-organic silicon hybrid structure epoxy resin composite (hydroxyl equivalent: 105mol/g) 44.99g is cured with resol.The shock strength of gained cured article is 21.52kJ/m
2, LOI is 36.9.
The comparative example 1
After the Resins, epoxy that contains melamine-organic silicon hybrid structure (N/Si-epoxy) that the present invention is prepared, 30 ℃ of bisphenol A type epoxy resins (E-51) were compound down, ' diaminodiphenyl-methane (DDM) was cured to add the solidifying agent 4,4 of stoichiometric quantity.So-called stoichiometric quantity refers to the amount of amino hydrogen in epoxy base unit weight in the compound system and solidifying agent 4, the 4 ' diaminodiphenyl-methane and calculates resulting 4, the 4 ' amounts of diaminodiphenyl-methane according to 1: 1 mol ratio.The epoxy resin cured product performance index that contain melamine-organic silicon hybrid structure are as shown in table 1.The preparation method of employed N/Si-epoxy is as follows in the table 1: according to the weight fraction meter, the formaldehyde solution of 100 parts of trimeric cyanamides and 193.05 part 37% was carried out hydroxymethylation 30 minutes under the PH=9 condition, add 374.60 parts of γ-glycidoxy Trimethoxy silane then and urge in 0.67g catalyzer osmanthus.
The result shows: under amine curing agent solidified, institute's synthetic contains melamine-organic silicon hybrid structure Resins, epoxy to be compared with bisphenol A type epoxy resin, and shock strength is brought up to 28.52kJ/m
2Limiting oxygen index(LOI) has improved nearly one times. and the shock strength of the prepared composite epoxy resin cured article that contains melamine-organic silicon hybrid structure Resins, epoxy and bisphenol A type epoxy resin formation is along with rising back downward trend appears in the raising performance that contains melamine-organic silicon hybrid structure Resins, epoxy add-on, and limiting oxygen index(LOI) then is simply to present trend of rising. illustrate that institute's synthetic melamine-organic silicon hybrid structure Resins, epoxy can obviously improve the mechanical property and the flame retardant properties of Resins, epoxy.
Table 1 contains melamine-organic silicon hybrid structure epoxy resin cured product performance index
| Sequence number | N/Si-epoxy | E-51 | DDM | Shock strength/kJ/m 2 | Limiting oxygen index(LOI) (LOI)/% |
| 1 | 100 | 0 | 11.65 | 28.52 | 39.8 |
| 2 | 0 | 100 | 25.13 | 10.80 | 19.8 |
| 3 | 10 | 100 | 26.30 | 18.20 | 24.8 |
| 4 | 30 | 100 | 28.63 | 15.47 | 29.6 |
| 5 | 50 | 100 | 30.96 | 12.85 | 35.8 |
The comparative example 2
The present invention is prepared contains melamine-organic silicon hybrid structure Resins, epoxy (N/Si-epoxy) and not only can be cured with the Ammonia solidifying agent, and can be cured with resol.Table 2 has provided the performance index that resol (PN) solidifies N/Si-epoxy and bisphenol A-type resol (Epoxy) cured article.Wherein the oxirane value of bisphenol-A phenolic Resins, epoxy is 0.44mol/100g, the hydroxyl equivalent of phenolic resin curative is 100, the preparation method of N/Si-epoxy is as follows: the formaldehyde solution of 100g trimeric cyanamide and 195g37% is mixed, regulate PH=9, reacted 20 minutes down at 80 ℃, and then add catalyzer triphenyl phosphorus 1.5g, and to phenmethyl glycidyl ether Trimethoxy silane 609.52g, reaction obtained containing melamine-organic silicon hybrid structure Resins, epoxy in 1 hour under 80 ℃.
The result shows: under the condition of resol as solidifying agent, the limiting oxygen index(LOI) that contains the composite epoxy resin of melamine-organic silicon hybrid Resins, epoxy and bisphenol A type epoxy resin formation increases along with the increase that contains the melamine-organic silicon hybrid structure amount of epoxy, shock strength then presents increases the trend that then reduces earlier. and illustrate under the certain condition of melamine-organic silicon hybrid structure epoxy resin content, make the mechanical property of Resins, epoxy and flame retardant resistance improve simultaneously.
Table 2 contains melamine-organic silicon hybrid structure epoxy resin cured product performance index
| Sequence number | N/Si-epoxy | Epoxy | PN | Shock strength/kJ/m 2 | Limiting oxygen index(LOI) (LOI)/% |
| 1 | 0 | 100 | 44.00 | 11.52 | 20.3 |
| 2 | 20 | 80 | 40.46 | 15.73 | 24.7 |
| 3 | 50 | 50 | 35.16 | 22.44 | 29.6 |
| 4 | 80 | 20 | 29.86 | 25.60 | 35.2 |
| 5 | 100 | 0 | 26.32 | 21.21 | 39.5 |
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 (9)
1. Resins, epoxy that contains melamine-organic silicon hybrid structure, it is characterized in that: it has general structure as the formula (1):
In the formula (1), R1, R2, R3, R4, R5, R6 be hydrogen or
And R1, R2, R3, R4, R5, R6 can not be a hydrogen simultaneously; R is
2. an a kind of preparation method who contains the Resins, epoxy of melamine-organic silicon hybrid structure according to claim 1 is characterized in that comprising the steps:
According to the weight part meter, with the massfraction of 100 parts trimeric cyanamides and 64.35-390 part be the formaldehyde solution of 20%-37% under the pH=7-10 condition in 60-90 ℃ of reaction 20-80 minute, add catalyzer and 150-1200 part epoxy radicals silicone hydride then at 60-100 ℃ of following hydrolysis-condensation reaction 1-5 hour.
3. a kind of preparation method who contains the Resins, epoxy of melamine-organic silicon hybrid structure according to claim 2 is characterized in that: the structure of used epoxy radicals silicone hydride as the formula (2):
In the formula (2), R ' is-CH
2CH
2CH
2-or-CH
2CH
2CH
2CH
2-;
R
1Be methyl, ethyl, n-propyl, sec.-propyl or butyl;
R
2Be methyl, ethyl, n-propyl, sec.-propyl or butyl;
N is 0 or 1.
4. according to claim 2 or the 3 described preparation methods that contain the Resins, epoxy of melamine-organic silicon hybrid structure, it is characterized in that: described catalyzer is a kind of in dibutyl tin dilaurate, triethylamine, triphenyl phosphorus, aluminum chloride, zinc dichloride or the iron trichloride.
5. according to claim 2 or the 3 described preparation methods that contain the Resins, epoxy of melamine-organic silicon hybrid structure, it is characterized in that: described catalyst consumption is the 0.05%-1% of reaction system material gross weight.
6. the preparation method who contains the Resins, epoxy of melamine-organic silicon hybrid structure according to claim 5 is characterized in that: described catalyst consumption is the 0.1-0.5% of reaction system material gross weight.
7. application that contains the Resins, epoxy of melamine-organic silicon hybrid structure according to claim 1 is characterized in that: be to mix use separately or with other Resins, epoxy;
Described other Resins, epoxy comprise bisphenol A type epoxy resin, bisphenol f type epoxy resin, any one or two kinds of above mixtures in the novolac epoxy.
8. the application that contains the Resins, epoxy of melamine-organic silicon hybrid structure according to claim 7, 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, and the oxirane value of novolac epoxy is 0.3-0.5mol/100g.
9. according to claim 7 or 8 each described application that contain the Resins, epoxy of melamine-organic silicon hybrid structure, it is characterized in that: add high-temperature curing agent during use;
Described high-temperature curing agent comprises amine curing agent, any one in Dyhard RU 100 class and the resol or two or more mixtures;
Described amine curing agent is a mphenylenediamine, Ursol D, m-xylene diamine, 4,4 ' diaminodiphenyl-methane or 4,4 ' diaminodiphenylsulfone(DDS)s;
Described Dyhard RU 100 class solidifying agent is a dicyandiamide;
Described phenolic resin curative is a resol, and hydroxyl equivalent is 90-160.
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Families Citing this family (11)
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| CN115181124A (en) * | 2022-08-12 | 2022-10-14 | 西华大学 | Self-migration flame-retardant waterproof compound and preparation method thereof |
| CN117126462A (en) * | 2023-08-28 | 2023-11-28 | 广州工程技术职业学院 | Graphene oxide/organic silicon/melamine hybrid flame-retardant epoxy resin and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005105939A1 (en) * | 2004-04-27 | 2005-11-10 | E.I. Dupont De Nemours And Company | Preparation and use of reactive organosilicon compounds |
| CN101108912A (en) * | 2007-06-05 | 2008-01-23 | 华东理工大学 | Flame-proof epoxy resin nano complexes material |
| CN101307155A (en) * | 2007-05-17 | 2008-11-19 | 财团法人工业技术研究院 | Fire retardant crosslinking agent and halogen free, non-phosphate and fire retardant epoxy resin composition |
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2009
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005105939A1 (en) * | 2004-04-27 | 2005-11-10 | E.I. Dupont De Nemours And Company | Preparation and use of reactive organosilicon compounds |
| CN101307155A (en) * | 2007-05-17 | 2008-11-19 | 财团法人工业技术研究院 | Fire retardant crosslinking agent and halogen free, non-phosphate and fire retardant epoxy resin composition |
| CN101108912A (en) * | 2007-06-05 | 2008-01-23 | 华东理工大学 | Flame-proof epoxy resin nano complexes material |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2001-123120A 2001.05.08 |
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Address after: 510650 Guangdong city of Guangzhou province Tianhe District Xing Branch Road No. 368 Patentee after: Guangzhou Chemistry Co., Ltd. Chinese Academy of Sciences Address before: 510650 Guangdong city of Guangzhou province Tianhe District Xing Branch Road No. 368 Patentee before: Guangzhou Inst. of Chemistry, Chinese Academy of Sciences |
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