CN106008919A - Phosphorus-containing flame-retardant epoxy resin having undergone hydrophobic modification by silane, and preparation method thereof - Google Patents
Phosphorus-containing flame-retardant epoxy resin having undergone hydrophobic modification by silane, and preparation method thereof Download PDFInfo
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- CN106008919A CN106008919A CN201610401985.8A CN201610401985A CN106008919A CN 106008919 A CN106008919 A CN 106008919A CN 201610401985 A CN201610401985 A CN 201610401985A CN 106008919 A CN106008919 A CN 106008919A
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- epoxy resin
- containing flame
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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Abstract
The invention relates to a phosphorus-containing flame-retardant epoxy resin having undergone hydrophobic modification by silane, and a preparation method thereof, belonging to the field of preparation of high-performance high polymer materials. The preparation method comprises the following steps: adding 20 to 40 g of DOPO-VTS, 100 to 150 g of DOPO type epoxy resin, 0.8 to 1.6 g of dibutyltin dilaurate (DBTL) and 0.5 to 4 g of deionized water into a 250-mL round-bottom flask equipped with a condenser tube; carrying out a reaction at 80 to 110 DEG C under stirring for 2 to 6 h; and then carrying out a vacuumized reaction for 0.5 to 2 h so as to obtain the yellow gummy phosphorus-containing flame-retardant epoxy resin (DV-m-DE) having undergone hydrophobic modification by silane. The epoxy resin prepared in the invention has excellent hydrophobicity and flame resistance; the vertical combustion grade of the epoxy resin reaches V-0 grade; the surface contact angle of the epoxy resin is increased to 92.7 to 106.3 DEG; and the epoxy resin has the characteristics of excellent compatibility, nontoxicity and environment friendliness, can be applied to outdoor or wet severe environments and has wide application prospects.
Description
Technical field
The invention belongs to the preparation field of high performance polymer material, be specifically related to the preparation method of a kind of silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin.
Background technology
Epoxy resin has good caking property, mechanicalness, electric insulating quality and chemical resistance, is widely used in many fields such as electronic and electrical equipment, transportation equipment, coating adhesive.But the fire resistance of ordinary epoxy resin is poor, there is serious disaster hidden-trouble.In order to improve the anti-flammability of epoxy resin, often dose halogen containing flame-retardant, but owing to the toxicity of halogen containing flame-retardant is relatively big, fire-retardant during easily produce secondary harm.Therefore, people start from halogen containing flame-retardant, sight is turned to organophosphorous fire retardant.Organophosphorous fire retardant shows splendid flame-retarding characteristic, and fire-retardant during the toxicant that produces few, become the developing direction of ethoxyline resin antiflaming.
Epoxy resin self polarity is relatively big, does not have hydrophobicity, adds organophosphorous fire retardant and can reduce the hydrophobicity of epoxy resin further.Research finds, under thunder and lightning weather, the hydrops of epoxy resin surface residual easily causes flicker and shelf depreciation, the most then accelerate epoxy resin aging, heavy then can make whole epoxy resin parts generation electrical breakdown.Additionally water or a kind of crazing initiator, if epoxy resin life-time service under high humidity environment, its mechanical property is also by severe exacerbation.The present invention is using organophosphor DOPO as fire retardant, using organosilan VTS as water-repelling agent; preparation is provided simultaneously with excellent flame retardancy and the hydrophobic compatibility is excellent, nontoxic, environmental-protection epoxy resin; it is possible not only to expand the application of epoxy resin, and there is important scientific meaning and obvious practical value.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin.Obtained silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin possesses anti-flammability and the hydrophobicity of excellence, and the compatibility is excellent, nontoxic, environmental protection, meets the current people requirement to ecological environmental protection, is a kind of preferably multi-functional epoxy resin.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin, it is with organophosphor DOPO as fire retardant, with organosilan VTS as water-repelling agent, by the method for chemical bonding, DOPO and VTS is grafted on epoxy resin, is described silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin.
Specifically include following steps:
20 ~ 40 g DOPO-VTS, 100 ~ 150 g DOPO type epoxy resin, 0.8 ~ 1.6 g dibutyl tin laurate (DBTL) and 0.5 ~ 4 g deionized water are joined equipped with in 250 mL round-bottomed flasks of condensing tube, 80 ~ 110 DEG C of stirring reaction 2 ~ 6 h, evacuation reaction 0.5 ~ 2 h, obtains yellow colloidal silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin (DV-m-DE) again.
Described DOPO-VTS is 9,10-dihydro-9-oxy miscellaneous-10-phospho hetero phenanthrene-10-oxide (DOPO) chemical bonding vinyltrimethoxy silane (VTS) forms, the mol ratio of DOPO:VTS is 1:1, with reference to the method such as Qian little Dong (research of design containing DOPO phosphorus silicon hybridization fire retardant and flame retardant epoxy thereof and carbamide resin performance. Hefei: China Science & Technology University, 2014 years).
Described DOPO type epoxy resin prepares with DOPO and E-51 epoxy resin for reaction raw materials, with reference to flood take on auspicious omen etc. method (preparation of DOPO type epoxy resin and fire resistance research. colloid and polymer, 2015,33 (1): 17-19).
Obtained silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin also needs to carry out cured, curing is: join in polytetrafluoroethylene beaker by 100 ~ 140 g DV-m-DE, 50 ~ 90 g firming agent and 0.4 ~ 0.8 g catalyst, after 40 ~ 80 DEG C of heated and stirred mix homogeneously, pour in preheated mould, put into and vacuum drying oven removes elevated cure after bubble, condition of cure is: 100 ~ 140 DEG C of insulation 1 ~ 3 h, 130 ~ 170 DEG C of insulation 6 ~ 10 h, after solidification terminates rear solidfied material furnace cooling, the demoulding samples.
Described firming agent is acid anhydride type curing agent, including any one in phthalic anhydride, 3,4,5,6-tetrabydrophthalic anhydrides, methyl tetrahydrophthalic anhydride, HHPA and methyl hexahydrophthalic anhydride.
Described catalyst is N, N-dimethyl benzylamine, N-benzyl pyrazine hexafluoro antimonate (N-benzylpyrazinium
Hexafluoroantimonate, BPH) and N-benzylquinolin hexafluoro antimonate (N-benzylquinoxalinium
Hexafluoroantimonate, BQH) in any one.
The remarkable advantage of the present invention is:
The present invention uses the method preparation of chemical bonding to be provided simultaneously with excellent flame retardancy and hydrophobic silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin.The vertical combustion grade of prepared epoxy resin reaches V-0 level, and surface contact angle brings up to 92.7 ° ~ 106.3 °, and epoxy inner is the most separated, shows that this epoxy resin has the compatibility of excellence.Meanwhile, prepared epoxy resin is nontoxic, meets the current people requirement to ecological environmental protection, is a kind of preferably multi-functional environment-protection epoxy resin.
Accompanying drawing explanation
Fig. 1 is the route map that the present invention prepares silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin (DV-m-DE)；
Fig. 2 is the profile scanning Electronic Speculum figure of silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin (DV-m-DE) solidfied material that the present invention prepares；
Fig. 3 is the infared spectrum of silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin (DV-m-DE) that the present invention prepares；
Fig. 4 is the hydrogen nuclear magnetic resonance spectrum of silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin (DV-m-DE) that the present invention prepares.
Detailed description of the invention
In order to make content of the present invention easily facilitate understanding, below in conjunction with detailed description of the invention, technical solutions according to the invention are described further, but the present invention is not limited only to this.
Embodiment 1
40 g DOPO-VTS, 100 g DOPO type epoxy resin, 0.8 g dibutyl tin laurate (DBTL) and 4 g deionized waters are joined equipped with in 250 mL round-bottomed flasks of condensing tube, 80 DEG C of stirring reaction 6 h, evacuation reacts 2 h again, obtains yellow colloidal silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin (DV-m-DE).
By 100 g DV-m-DE, 50 g methyl tetrahydrophthalic anhydrides and 0.4 g N, N-dimethyl benzylamine joins in polytetrafluoroethylene beaker, after 40 DEG C of heated and stirred mix homogeneously, pour in preheated mould, putting into and remove elevated cure after bubble in vacuum drying oven, condition of cure is: 100 DEG C of insulation 3 h, 130 DEG C of insulation 10 h, after solidfied material furnace cooling, the demoulding samples.
The vertical combustion grade of this epoxy resin reaches V-0 level, and surface contact angle is 106.3 °.
Embodiment 2
20 g DOPO-VTS, 150 g DOPO type epoxy resin, 1.6 g dibutyl tin laurates (DBTL) and 0.5 g deionized water are joined equipped with in 250 mL round-bottomed flasks of condensing tube, 110 DEG C of stirring reaction 2 h, evacuation reacts 0.5 h again, obtains yellow colloidal silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin (DV-m-DE).
140 g DV-m-DE, 90 g HHPAs and 0.8 g N-benzyl pyrazine sodium hexafluoroantimonate are joined in polytetrafluoroethylene beaker, after 80 DEG C of heated and stirred mix homogeneously, pours in preheated mould, put into and vacuum drying oven removes elevated cure after bubble；Condition of cure is: 140 DEG C of insulation 1 h, and 170 DEG C of insulation 6 h, after solidfied material furnace cooling, the demoulding samples.
The vertical combustion grade of this epoxy resin reaches V-0 level, and surface contact angle is 92.7 °.
Embodiment 3
30 g DOPO-VTS, 130 g DOPO type epoxy resin, 1.2 g dibutyl tin laurates (DBTL) and 2 g deionized waters are joined equipped with in 250 mL round-bottomed flasks of condensing tube, 100 DEG C of stirring reaction 4 h, evacuation reacts 1 h again, obtains yellow colloidal silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin (DV-m-DE).
By 120 g DV-m-DE, 70 g 3,4,5,6-tetrabydrophthalic anhydrides and 0.6 g N-benzylquinolin sodium hexafluoroantimonate join in polytetrafluoroethylene beaker, after 60 DEG C of heated and stirred mix homogeneously, pour in preheated mould, putting into and remove elevated cure after bubble in vacuum drying oven, condition of cure is: 120 DEG C of insulation 2 h, 150 DEG C of insulation 8 h, after solidfied material furnace cooling, the demoulding samples.
The vertical combustion grade of this epoxy resin reaches V-0 level, and surface contact angle is 97.1 °.
From figure 3, it can be seen that in the infrared absorpting light spectra of DOPO-VTS, 2841cm-1The absworption peak at place belongs to the C-H stretching vibration absworption peak of methoxyl group；In the infrared absorpting light spectra of DV-m-DE, above-mentioned absworption peak disappears, and illustrates that the methoxyl group of DOPO-VTS take part in reaction completely.Simultaneously at 1100cm-1Near occur in that widthization folds peak, illustrate that DOPO-VTS hydrolytic condensation creates Si-O-Si key.
From fig. 4, it can be seen that in the hydrogen nuclear magnetic resonance spectrum of DOPO-VTS, be the chemical shift of methoxyl group hydrogen at 3.46ppm；In the hydrogen nuclear magnetic resonance spectrum of DV-m-DE, the chemical shift of methoxyl group hydrogen disappears, and illustrates that methoxyl group take part in reaction completely.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent and modification, all should belong to the covering scope of the present invention.
Claims (6)
1. a silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin, it is characterized in that: described silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin is with organophosphor DOPO as fire retardant, with organosilan VTS as water-repelling agent, by the method for chemical bonding, DOPO and VTS is grafted on epoxy resin.
2. the method preparing silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin as claimed in claim 1, it is characterised in that: comprise the following steps:
By 20 ~ 40 g DOPO-VTS, 100 ~ 150
G DOPO type epoxy resin, 0.8 ~ 1.6 g dibutyl tin laurate and 0.5 ~ 4 g deionized water join equipped with in 250 mL round-bottomed flasks of condensing tube, 80 ~ 110 DEG C of stirring reaction 2 ~ 6 h, evacuation reaction 0.5 ~ 2 h, obtains yellow colloidal silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin again.
The preparation method of silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin the most according to claim 2, it is characterised in that: after preparing silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin, also needing to carry out cured, concrete curing is as follows:
By 100 ~ 140 g silane hydrophobically modified phosphorus-containing flame-retardant epoxy resins, 50 ~ 90
G firming agent and 0.4 ~ 0.8 g catalyst join in polytetrafluoroethylene beaker, and 40 ~ 80
After DEG C heated and stirred mix homogeneously, pouring in preheated mould, put into and remove elevated cure after bubble in vacuum drying oven, after solidification terminates rear solidfied material furnace cooling, the demoulding samples.
The preparation method of silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin the most according to claim 3, it is characterized in that: described firming agent is acid anhydride type curing agent, including phthalic anhydride, 3,4, any one in 5,6-tetrabydrophthalic anhydrides, methyl tetrahydrophthalic anhydride, HHPA and methyl hexahydrophthalic anhydride.
The preparation method of silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin the most according to claim 3, it is characterised in that: described catalyst is any one in N, N-dimethyl benzylamine, N-benzyl pyrazine hexafluoro antimonate and N-benzylquinolin hexafluoro antimonate.
The preparation method of silane hydrophobically modified phosphorus-containing flame-retardant epoxy resin the most according to claim 3, it is characterised in that: condition of cure is: 100 ~ 140 DEG C of insulation 1 ~ 3 h, 130 ~ 170 DEG C of insulation 6 ~ 10 h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519189A (en) * | 2016-11-05 | 2017-03-22 | 福州大学 | Epoxy silicone oil modified phosphorus-containing flame-retardant epoxy resin and preparation method thereof |
| CN107177169A (en) * | 2017-06-29 | 2017-09-19 | 倪群 | A kind of rich phosphaization grafting flame retardant epoxy material and preparation method thereof |
| CN107177168A (en) * | 2017-06-29 | 2017-09-19 | 倪群 | A kind of hydridization is grafted anti-oxidant flame retardant epoxy material and preparation method thereof |
| CN107201002A (en) * | 2017-06-29 | 2017-09-26 | 倪群 | A kind of carbon nano-tube hybridization grafting flame retardant epoxy material and preparation method thereof |
| CN107216611A (en) * | 2017-06-29 | 2017-09-29 | 倪群 | A kind of shock resistance hydridization grafting flame retardant epoxy material and preparation method thereof |
| CN109280164A (en) * | 2018-07-28 | 2019-01-29 | 南京艾利克斯电子科技有限公司 | A kind of coating material and preparation method thereof with ultra-hydrophobicity |
| TWI669307B (en) * | 2017-12-27 | 2019-08-21 | 大陸商廣東生益科技股份有限公司 | Phosphate-containing active ester, preparation method thereof, flame retardant resin composition, prepreg and metal foil-clad laminate |
| CN110511354A (en) * | 2019-08-30 | 2019-11-29 | 苏州科技大学 | A kind of phosphorus silicon synergistic fire retardant and preparation method thereof containing epoxy group |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519189A (en) * | 2016-11-05 | 2017-03-22 | 福州大学 | Epoxy silicone oil modified phosphorus-containing flame-retardant epoxy resin and preparation method thereof |
| CN106519189B (en) * | 2016-11-05 | 2018-08-17 | 福州大学 | A kind of phosphorus-containing flame-retardant epoxy resin and preparation method thereof that epoxy silicon oil is modified |
| CN107177169A (en) * | 2017-06-29 | 2017-09-19 | 倪群 | A kind of rich phosphaization grafting flame retardant epoxy material and preparation method thereof |
| CN107177168A (en) * | 2017-06-29 | 2017-09-19 | 倪群 | A kind of hydridization is grafted anti-oxidant flame retardant epoxy material and preparation method thereof |
| CN107201002A (en) * | 2017-06-29 | 2017-09-26 | 倪群 | A kind of carbon nano-tube hybridization grafting flame retardant epoxy material and preparation method thereof |
| CN107216611A (en) * | 2017-06-29 | 2017-09-29 | 倪群 | A kind of shock resistance hydridization grafting flame retardant epoxy material and preparation method thereof |
| TWI669307B (en) * | 2017-12-27 | 2019-08-21 | 大陸商廣東生益科技股份有限公司 | Phosphate-containing active ester, preparation method thereof, flame retardant resin composition, prepreg and metal foil-clad laminate |
| CN109280164A (en) * | 2018-07-28 | 2019-01-29 | 南京艾利克斯电子科技有限公司 | A kind of coating material and preparation method thereof with ultra-hydrophobicity |
| CN110511354A (en) * | 2019-08-30 | 2019-11-29 | 苏州科技大学 | A kind of phosphorus silicon synergistic fire retardant and preparation method thereof containing epoxy group |
| CN110511354B (en) * | 2019-08-30 | 2021-11-16 | 苏州科技大学 | Phosphorus-silicon synergistic flame retardant containing epoxy group and preparation method thereof |
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