CN104829862A - Organic phosphine silane coupling agent and preparing method thereof - Google Patents
Organic phosphine silane coupling agent and preparing method thereof Download PDFInfo
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Abstract
The invention relates to a surface modifier for enhanced fiber materials, in particular to organic phosphine silane coupling agent and a preparing method thereof. A molecular structural formula of the organic phosphine silane coupling agent is shown below. The preparing method includes: dissolving silane coupling agent in organic solvent, adding acid-binding agent, dropwise adding organic phosphonic chloride under ice bath and nitrogen conditions, and after reaction, filtering a product to remove sediment so as to obtain the organic phosphine silane coupling agent. By modifying the enhanced fibers with the organic phosphine silane coupling agent, interfacial compatibility of the fibers and polymer materials can be improved, and fiber reinforced polymer composite materials are better in mechanical property; the fibers can be imparted certain flame retardance substantially, during combustion of the composite materials, the organic phosphine silane coupling agent catalyzes polymer carbonization on the surface of the fibers, surface roughening of the fibers is promoted, a transfer passage of combustible molecules is cut off, and the candlewick effect of the fibers is suppressed accordingly.
Description
Technical field
The present invention relates to a kind of surface-modifying agent of enhanced fiber material, specifically relate to a kind of organic phosphine silane coupling agent and preparation method thereof.
Background technology
Fiber reinforced polymer matrix composite is light with quality, specific tenacity is high, specific modulus advantages of higher, obtains a wide range of applications.But most of enhanced fiber surface presentation unreactiveness, when reinforcement as polymer materials, the poor compatibility between itself and polymkeric substance, bonding force are weak, and the matrix material prepared is difficult to the mechanical property giving full play of fiber excellence.In order to overcome this defect, silane coupling agent is generally adopted to carry out modifying interface to improve the mechanical property of composite product to fiber at present.
Polymkeric substance is a kind of inflammable material, and the fire hazard of fiber reinforced polymer matrix composite will much larger than non-reinforcing material, because this material is in combustion because the impact being subject to fiber " candle wick " effect is difficult to extinguish.Although the fiber after modifying with silane coupling agent can be applied in the enhancing modified of polymkeric substance, silane coupling agent is a kind of very inflammable small molecular organic compounds, can aggravate " candle wick " effect in the combustion processes of fibre reinforced composites.At present, " candle wick " effect of suppression fiber, the flame retardant properties of raising matrix material are mainly realized by interpolation fire retardant.Such as US Patent No. 6365071B1, US6255371 B1 and US6547992 B1 mention the main flame retardant using diethyl hypophosphite as matrix material, Chinese patent CN 1019288448B and CN 102174247A reports and adopts inorganic hypophosphite to be main flame retardant, these fire retardants all have such as formula the structure (wherein R is the identical M such as hydrogen atom, alkyl, aryl is atoms metal, and n is the valency of M) shown in (1).Although these fire retardants have good flame retardant effect in the composite, addition is higher, causes serious harm to the mechanical property of material.
Therefore, " candle wick " effect of fiber is suppressed to need to carry out fire-retardant finish to fiber surface.Adopting flame retardant modified silane coupler to carry out fire-retardant finish to fiber is a kind of feasible method.Flame retardant modified silane coupler is existing relevant report at present.As Chinese patent CN 101613370A reports a kind of flame retardant modified silane coupler of phosphorus-nitrogen containing, Chinese patent CN 101792537A reports a kind of silane coupling agent containing DOPO group.But the undeclared flame retardant modified silane coupler of these patents is to the surface treatment of the polymkeric substance such as glass fibre, basalt fibre enhanced fiber and flame retardant effect thereof.
Summary of the invention
The technical problem to be solved in the present invention be overcome fiber " candle wick " effect existed in prior art be difficult to suppress significant deficiency, a kind of mechanical property that both can improve fiber reinforced polymer composites is provided, " candle wick " effect of fiber to be modified can be suppressed again to give the organic phosphine silane coupling agent of the certain flame retardant properties of fiber.
Another technical problem that the present invention will solve is for providing a kind of preparation method of above-mentioned organic phosphine silane coupling agent.
Organic phosphine silane coupling agent of the present invention, its molecular structural formula is:
In formula, R
1for methoxy or ethoxy, R
2for ethyl or phenyl.
The preparation method of organic phosphine silane coupling agent of the present invention, reaction raw materials is made up of silane coupling agent, acid binding agent, organic phosphine acyl chlorides and organic solvent, acid binding agent and silane coupling agent mol ratio are 0.5 ~ 1.5: 1, and organic phosphine acyl chlorides and silane coupling agent mol ratio are 1: 1;
Described silane coupling agent is selected from γ-aminopropyltrimethoxysilane or γ-aminopropyl triethoxysilane;
Described acid binding agent is selected from triethylamine or pyridine;
Described organic phosphine acyl chlorides is selected from diethyl time phosphonyl chloride or diphenyl phosphinyl chloride;
Described solvent is selected from tetrahydrofuran (THF), methylene dichloride or N,N-dimethylacetamide.
The preparation method of organic phosphine silane coupling agent of the present invention, its concrete reactions steps is: be first dissolved in organic solvent by silane coupling agent, then acid binding agent is added, under ice bath and condition of nitrogen gas, dropwise add organic phosphine acyl chlorides, after dropwising, then under condition of ice bath, continue reaction 1 ~ 4 hour, then 30 ~ 60 DEG C are warming up to, condition of nitrogen gas reaction 8 ~ 10 hours, desolventize after finally products therefrom being crossed elimination precipitation, obtain organic phosphine silane coupling agent of the present invention.
Organic phosphine silane coupling agent of the present invention and preparation method thereof, shows relative to the beneficial effect of prior art:
1), adopt the silane coupler modified enhanced fiber of organic phosphine of the present invention, the interface compatibility of fiber and polymer materials can be improved, improve the mechanical property of fiber reinforced polymer composites.
2) the silane coupler modified enhanced fiber of organic phosphine of the present invention, is adopted, can inherently give fiber certain flame retardant properties, make matrix material in combustion, organic phosphine silane coupling agent is in the carbonization of fiber surface catalytic polymer, promote fiber surface roughening, cut off the Transfer pipe of flammable molecule, and then suppress " candle wick " effect of fiber.Coordinate a small amount of fire retardant additive without halogen, the flame retardant properties of matrix material can be improved further.
3), the preparation method of organic phosphine silane coupling agent of the present invention is simple, with low cost, has wide market application foreground.
Accompanying drawing explanation
Fig. 1 is the infrared spectra of target product prepared by embodiment 1.
Fig. 2 is the proton nmr spectra of target product prepared by embodiment 1.
Embodiment
Below in conjunction with accompanying drawing, optimal way of the present invention is described in further detail.
Embodiment 1
11.07 grams of γ-aminopropyl triethoxysilanes, 5.06 grams of triethylamines and 100 milliliters of tetrahydrofuran (THF)s are placed in there-necked flask, under ice bath and condition of nitrogen gas, dropwise add 11.8 grams of diphenyl phosphinyl chlorides, under ice bath and condition of nitrogen gas, reaction 2 hours is continued after dropwising, then 40 DEG C are warming up to, react 8 hours in condition of nitrogen gas, desolventize after finally products therefrom being crossed elimination precipitation, the light yellow transparent liquid obtained is organic phosphine silane coupling agent of the present invention.
Infrared spectroscopy (KBr, cm
-1): 3200-3500 (amino N-H), 3050-3100,911-948 (phenyl ring C-H), 2873-2976,1437,1390 (CH
3-and-CH
2-), 1584-1640 (phenyl ring C=C), 1201 (P=O), 1090 (Si-O).Infrared spectra is shown in accompanying drawing 1.
Hydrogen nuclear magnetic resonance spectrum analysis (
1hNMR, CDCl
3, δ, ppm, TMS): 0.61-0.70 (Si-CH between 2H, Si and N
2-), 1.09-1.28 (9H, CH in oxyethyl group
3-), 1.64-1.83 (the m-CH of 2H, Si and N
2-), 2.94-3.13 (N-CH between 2H, Si and N
2-), 3.69-3.88 (6H ,-CH in oxyethyl group
2-), 7.40-7.97 (10H, C-H in phenyl ring).Proton nmr spectra is shown in accompanying drawing 2.
Fire-retardant and Mechanics Performance Testing:
Respectively 10 grams of choppeds are soaked in the ethanolic soln of organic phosphine silane coupling agent prepared by the present embodiment containing 30wt%, containing in the ethanolic soln of the γ-aminopropyl triethoxysilane of 30wt% 4 hours, then be placed in 100 DEG C of baking ovens to dry 1 hour, obtain the glass fibre of two kinds of modifier treatments, be expressed as GF-1 and GF-2.GF-1 and GF-2 obtained as stated above is added respectively in polybutylene terephthalate (PBT) and polymeric amide (PA) and prepare matrix material PBT/GF-1, PBT/GF-2, PA/GF-1, PA/GF-2, keep the content of glass fibre to be 30wt%.
Adopt cone calorimetry, limiting oxygen index(LOI) tester and universal testing machine to test the heat release rate of above-mentioned sample, total Thermal release, tensile strength and tensile modulus, test result lists in table 1:
Table 1
Can be found out by the test data contrast of table 1, the glass fibre of organic phosphine silane coupling agent process obtained in the present embodiment significantly can reduce the heat release rate of matrix material and total Thermal release, improves the limiting oxygen index(LOI) of matrix material.Flame retardant properties test result shows, organic phosphine silane coupling agent obtained in the present embodiment has fire retardation, can suppress " candle wick " effect of fiber.Meanwhile, tensile strength change is little, shows that the mechanical property of matrix material is uninfluenced.
Embodiment 2
11.07 grams of γ-aminopropyl triethoxysilanes, 5.93 grams of pyridines and 100 milliliters of methylene dichloride are placed in there-necked flask, under ice bath and condition of nitrogen gas, dropwise add 7.03 grams of diethyl time phosphonyl chloride, under ice bath and condition of nitrogen gas, reaction 1 hour is continued after dropwising, then 30 DEG C are warming up to, react 9 hours in condition of nitrogen gas, desolventize after finally products therefrom being crossed elimination precipitation, the light yellow transparent liquid obtained is organic phosphine silane coupling agent of the present invention.
Infrared spectroscopy (KBr, cm
-1): 3200-3500 (amino N-H), 3050-3100,910-950 (phenyl ring C-H), 2870-2980,1435,1393 (CH
3-and-CH
2-), 1200 (P=O), 1091 (Si-O).
Hydrogen nuclear magnetic resonance spectrum analysis (
1hNMR, CDCl
3, δ, ppm, TMS): 0.62-0.74 (Si-CH between 2H, Si and N
2-), 0.90-1.03 (6H, P-CH
2-CH
3middle CH
3-), 1.11-1.30 (9H, CH in oxyethyl group
3-), 1.64-1.83 (the m-CH of 2H, Si and N
2-), 1.95-2.21 (4H, P-CH
2-CH
3in-CH
2-), 12.94-3.13 (N-CH between 2H, Si and N
2-), 3.69-3.88 (6H ,-CH in oxyethyl group
2-).
Fire-retardant and Mechanics Performance Testing:
Respectively 10 grams of short yarn cuttings of basalt fibre are soaked in the ethanolic soln of organic phosphine silane coupling agent prepared by the present embodiment containing 30wt%, containing in the ethanolic soln of the γ-aminopropyl triethoxysilane of 30wt% 4 hours, then be placed in 100 DEG C of baking ovens to dry 1 hour, obtain the basalt fibre of two kinds of modifier treatments, be expressed as BF-1 and BF-2.BF-1 and BF-2 obtained as stated above is added respectively in polymeric amide (PA) and poly(lactic acid) (PLA) and prepare matrix material PA/BF-1, PA/BF-2, PLA/BF-1, PLA/BF-2, keep the content of basalt fibre to be 20wt%.
Adopt cone calorimetry, limiting oxygen index(LOI) tester and universal testing machine to test the heat release rate of above-mentioned sample, total Thermal release, tensile strength and tensile modulus, test result lists in table 2:
Table 2
Can be found out by the test data contrast of table 2, the basalt fibre of organic phosphine silane coupling agent process obtained in the present embodiment significantly can reduce the heat release rate of matrix material and total Thermal release, improves the limiting oxygen index(LOI) of matrix material.Flame retardant properties test result shows, organic phosphine silane coupling agent obtained in the present embodiment has fire retardation, can suppress " candle wick " effect of fiber.Meanwhile, tensile strength change is little, shows that the mechanical property of matrix material is uninfluenced.
Embodiment 3
By 8.96 grams of γ-aminopropyltrimethoxysilanes, 2.53 grams of triethylamines and 100 milliliters of N, N-N,N-DIMETHYLACETAMIDE is placed in there-necked flask, under ice bath and condition of nitrogen gas, dropwise add 11.83 grams of diphenyl phosphinyl chlorides, under ice bath and condition of nitrogen gas, continue reaction 3 hours after dropwising, be then warming up to 50 DEG C, react 9 hours in condition of nitrogen gas, desolventize after finally products therefrom being crossed elimination precipitation, the light yellow transparent liquid obtained is organic phosphine silane coupling agent of the present invention.
Infrared spectroscopy (KBr, cm
-1): 3200-3500 (amino N-H), 3050-3100,910-945 (phenyl ring C-H), 2871-2979,1437,1390 (CH
3-and-CH
2-), 1582-1640 (phenyl ring C=C), 1202 (P=O), 1088 (Si-O).
Hydrogen nuclear magnetic resonance spectrum analysis (
1hNMR, CDCl
3, δ, ppm, TMS): 0.62-0.71 (Si-CH between 2H, Si and N
2-), 1.64-1.83 (the m-CH of 2H, Si and N
2-), 2.91-3.15 (N-CH between 2H, Si and N
2-), 3.61-3.85 (9H, CH in methoxyl group
3-), 7.45-7.98 (10H, C-H in phenyl ring).
Fire-retardant and Mechanics Performance Testing:
Respectively 10 grams of short yarn cuttings of basalt fibre are soaked in the ethanolic soln of organic phosphine silane coupling agent prepared by the present embodiment containing 30wt%, containing in the ethanolic soln of the γ-aminopropyltrimethoxysilane of 30wt% 4 hours, then be placed in 100 DEG C of baking ovens to dry 1 hour, obtain the basalt fibre of two kinds of modifier treatments, be expressed as BF-1 and BF-2.BF-1 and BF-2 obtained as stated above is added respectively in polymeric amide (PA) and poly(lactic acid) (PLA) and prepare matrix material PA/BF-1, PA/BF-2, PLA/BF-1, PLA/BF-2, keep the content of basalt fibre to be 20wt%.
Adopt cone calorimetry, limiting oxygen index(LOI) tester and universal testing machine to test the heat release rate of above-mentioned sample, total Thermal release, tensile strength and tensile modulus, test result lists in table 3:
Table 3
Can be found out by the test data contrast of table 3, the basalt fibre of organic phosphine silane coupling agent process obtained in the present embodiment significantly can reduce the heat release rate of matrix material and total Thermal release, improves the limiting oxygen index(LOI) of matrix material.Flame retardant properties test result shows, organic phosphine silane coupling agent obtained in the present embodiment has fire retardation, can suppress " candle wick " effect of fiber.Meanwhile, tensile strength change is little, shows that the mechanical property of matrix material is uninfluenced.
Embodiment 4
8.96 grams of γ-aminopropyltrimethoxysilanes, 3.96 grams of pyridines and 100 milliliters of tetrahydrofuran (THF)s are placed in there-necked flask, under ice bath and condition of nitrogen gas, dropwise add 7.03 grams of diethyl time phosphonyl chloride, under ice bath and condition of nitrogen gas, reaction 4 hours is continued after dropwising, then 60 DEG C are warming up to, react 10 hours in condition of nitrogen gas, desolventize after finally products therefrom being crossed elimination precipitation, the light yellow transparent liquid obtained is organic phosphine silane coupling agent of the present invention.
Infrared spectroscopy (KBr, cm
-1): 3200-3500 (amino N-H), 3050-3100,910-948 (phenyl ring C-H), 2873-2980,1438,1394 (CH
3-and-CH
2-), 1201 (P=O), 1086 (Si-O).
Hydrogen nuclear magnetic resonance spectrum analysis (
1hNMR, CDCl
3, δ, ppm, TMS): 0.61-0.71 (Si-CH between 2H, Si and N
2-), 0.91-1.01 (6H, P-CH
2-CH
3middle CH
3-), 1.65-1.85 (the m-CH of 2H, Si and N
2-), 1.92-2.27 (4H, P-CH
2-CH
3in-CH
2-), 2.91-3.15 (N-CH between 2H, Si and N
2-), 3.63-3.82 (9H, CH in methoxyl group
3-).
Fire-retardant and Mechanics Performance Testing:
Respectively 10 grams of choppeds are soaked in the ethanolic soln of organic phosphine silane coupling agent prepared by the present embodiment containing 30wt%, containing in the ethanolic soln of the γ-aminopropyltrimethoxysilane of 30wt% 4 hours, then be placed in 100 DEG C of baking ovens to dry 1 hour, obtain the glass fibre of two kinds of modifier treatments, be expressed as GF-1 and GF-2.GF-1 and GF-2 obtained as stated above is added respectively in polybutylene terephthalate (PBT) and polymeric amide (PA) and prepare matrix material PBT/GF-1, PBT/GF-2, PA/GF-1, PA/GF-2, keep the content of glass fibre to be 30wt%.
Adopt cone calorimetry, limiting oxygen index(LOI) tester and universal testing machine to test the heat release rate of above-mentioned sample, total Thermal release, tensile strength and tensile modulus, test result lists in table 4:
Table 4
Can be found out by the test data contrast of table 4, the glass fibre of organic phosphine silane coupling agent process obtained in the present embodiment significantly can reduce the heat release rate of matrix material and total Thermal release, improves the limiting oxygen index(LOI) of matrix material.Flame retardant properties test result shows, organic phosphine silane coupling agent obtained in the present embodiment has fire retardation, can suppress " candle wick " effect of fiber.Meanwhile, tensile strength change is little, shows that the mechanical property of matrix material is uninfluenced.
The various embodiments described above, just in order to technical conceive of the present invention and feature are described, its objective is and are one of ordinary skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.The change of every equivalence done by the essence of content of the present invention or modification, all should be encompassed in protection scope of the present invention.
Claims (3)
1. an organic phosphine silane coupling agent, is characterized in that its molecular structural formula is:
In formula, R
1for methoxy or ethoxy, R
2for ethyl or phenyl.
2. prepare the method for organic phosphine silane coupling agent as claimed in claim 1, it is characterized in that: reaction raw materials is made up of silane coupling agent, acid binding agent, organic phosphine acyl chlorides and organic solvent, acid binding agent and silane coupling agent mol ratio are 0.5 ~ 1.5: 1, and organic phosphine acyl chlorides and silane coupling agent mol ratio are 1: 1;
Described silane coupling agent is selected from γ-aminopropyltrimethoxysilane or γ-aminopropyl triethoxysilane;
Described acid binding agent is selected from triethylamine or pyridine;
Described organic phosphine acyl chlorides is selected from diethyl time phosphonyl chloride or diphenyl phosphinyl chloride;
Described solvent is selected from tetrahydrofuran (THF), methylene dichloride or N,N-dimethylacetamide.
3. preparation method as claimed in claim 2, it is characterized in that: first silane coupling agent is dissolved in organic solvent, then acid binding agent is added, under ice bath and condition of nitrogen gas, dropwise add organic phosphine acyl chlorides, after dropwising, then under condition of ice bath, continue reaction 1 ~ 4 hour, then 30 ~ 60 DEG C are warming up to, condition of nitrogen gas reaction 8 ~ 10 hours, desolventize after finally products therefrom being crossed elimination precipitation, obtain organic phosphine silane coupling agent.
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| CN105862416A (en) * | 2016-05-16 | 2016-08-17 | 安徽天恩旅行用品科技有限公司 | Method for manufacturing fluorescent fabric for children's bags |
| CN105860358A (en) * | 2016-05-16 | 2016-08-17 | 安徽天恩旅行用品科技有限公司 | Method for manufacturing PVC (Polyvinyl Chloride) luggage material |
| CN105908486A (en) * | 2016-05-16 | 2016-08-31 | 安徽天恩旅行用品科技有限公司 | Method for producing fluorescent fabric for medical first-aid kit |
| CN106003942A (en) * | 2016-05-16 | 2016-10-12 | 安徽天恩旅行用品科技有限公司 | Manufacturing method of luggage leather |
| CN108101939A (en) * | 2017-12-27 | 2018-06-01 | 北京工商大学 | The method and its application in flame retardant polyurethane that a kind of phosphorus-Silica hydrogel and induction APP decompose fast rapid-result charcoal in advance |
| CN110845529A (en) * | 2019-11-23 | 2020-02-28 | 合肥学院 | Phosphorus-containing polyethylene polyamine flame retardant and preparation method thereof |
| CN115260681A (en) * | 2022-09-29 | 2022-11-01 | 江苏潮启新材料科技有限公司 | Impact-resistant flame-retardant decorative film and preparation method thereof |
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| CN105862416A (en) * | 2016-05-16 | 2016-08-17 | 安徽天恩旅行用品科技有限公司 | Method for manufacturing fluorescent fabric for children's bags |
| CN105860358A (en) * | 2016-05-16 | 2016-08-17 | 安徽天恩旅行用品科技有限公司 | Method for manufacturing PVC (Polyvinyl Chloride) luggage material |
| CN105908486A (en) * | 2016-05-16 | 2016-08-31 | 安徽天恩旅行用品科技有限公司 | Method for producing fluorescent fabric for medical first-aid kit |
| CN106003942A (en) * | 2016-05-16 | 2016-10-12 | 安徽天恩旅行用品科技有限公司 | Manufacturing method of luggage leather |
| CN108101939A (en) * | 2017-12-27 | 2018-06-01 | 北京工商大学 | The method and its application in flame retardant polyurethane that a kind of phosphorus-Silica hydrogel and induction APP decompose fast rapid-result charcoal in advance |
| CN108101939B (en) * | 2017-12-27 | 2020-08-18 | 北京工商大学 | Phosphorus-silicon gel, method for inducing advanced decomposition of APP (application) to quickly form carbon and application of phosphorus-silicon gel in flame-retardant polyurethane |
| CN110845529A (en) * | 2019-11-23 | 2020-02-28 | 合肥学院 | Phosphorus-containing polyethylene polyamine flame retardant and preparation method thereof |
| CN110845529B (en) * | 2019-11-23 | 2024-02-09 | 合肥学院 | Phosphorus-containing polyethylene polyamine flame retardant and preparation method thereof |
| CN115260681A (en) * | 2022-09-29 | 2022-11-01 | 江苏潮启新材料科技有限公司 | Impact-resistant flame-retardant decorative film and preparation method thereof |
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Application publication date: 20150812 |