CN102731543A - Siliceous N-substituted alkyloxy hindered amine compound and its preparation method - Google Patents
Siliceous N-substituted alkyloxy hindered amine compound and its preparation method Download PDFInfo
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Abstract
The invention discloses a siliceous N-substituted alkyloxy hindered amine compound and its preparation method, wherein the constitutional unit of the compound is as shown in the formula I. In the formula I, X is the element O or group R, wherein the structural formula of the group R is as shown in the formula II. In the formula II, the general formula of R1 is -HN(CH2CH2NH)n(CH2)3-, wherein n is 0-2; R2 is an alkyl group, the general formula of which is -CmH2m+1, wherein m is1-8; R3 is an alkyl group, the general formula of which is -CkH2k-, wherein k is 1-6; R4 and R5 respectively represent an alkyl group, of which the general formula is -CiH2i+1 or a cycloalkyl group, of which the general formula is -CtH2t, wherein i is 1-8 and t is 1-8. The compound simultaneously has flame-retardation synergy, light stability and compatibilization, can be used to raise flame retardation of a flame-retardation polymer and simultaneously further improve its light stability, mechanical property and the like.
Description
Technical field
The present invention relates to a kind of hindered amine fire retarding synergist and compound method thereof, be specifically related to a kind of siliceous type N-substituted alkoxy hindered amine compound and compound method thereof.
Background technology
In recent years, find that as the hindered amine of photostabilizer N-substituted alkoxy hindered amine has excellent flame-retardant in the improved performance process for a long time.N-substituted alkoxy hindered amine improves a kind of in the kind as hindered amine, has the characteristics of low reactivity, and its chemical structure of general formula is:
Wherein, A is for connecting the auxiliary group of piperidyl, and B is a substituted alkyl.
The flame retardant efficiency of N-substituted alkoxy hindered amine in polyolefine mainly is the radical that the free radical scavenger of the efficient recyclable regenerative that produces through combustion decomposition disturbs and suppresses to produce in the combustion processes, and makes it to be converted into that compounds such as metastable alcohol, ketone realize.Research shows that N-substituted alkoxy hindered amine is applied to the thin goods of polyolefine such as fiber and film etc. embody excellent fire retardant efficient, and low dense efficient, adds about 0.5% and can reach satisfied flame retardant properties.Simultaneously, its good fire-retardant synergistic effect can significantly reduce the consumption of conventional flame retardant.Traditional N-substituted alkoxy hindered amine is generally the lower small molecules of molecular weight.Because lower molecular weight, it causes aspects such as being prone to migration, volatile and extracting easily in polymer materials deficiency causes effect faint thereby reduced its effective concentration in polymkeric substance.Be shown in the patent US 5844026 of Switzerland Ciba company (Ciba Specialty Chemicals) the earliest about the report of the synthetic aspect of this based flame retardant.1998, the said firm released N-substituted alkoxy hindered amines fire retardant Flamestab NOR 116 (referring to patent WO 2005005388, WO 2008003605) first, but it needs condition and synthesis technique complicacies such as HTHP.
Summary of the invention
The objective of the invention is to overcome the part or all of defective of prior art and a kind of new siliceous type N-substituted alkoxy hindered amine compound and compound method thereof be provided.
Prior art is applied to polymeric system with N-substituted alkoxy hindered amine as fire retarding synergist, has considered that morely N-substituted alkoxy hindered amine is in the contribution aspect steady of fire-retardant and light.And inventive concept of the present invention is: consider that silane coupling agent is an one type of silane that contains two kinds of different chemical character groups in the molecule simultaneously; Through coupling together the interface of two kinds of opposed polarity materials; Silane coupling agent can significantly improve the consistency of inorganic combustion inhibitor and polymeric matrix, thereby can improve the mechanical property of flame-retardant polymer system significantly; Simultaneously, through forming Si-O-C and Si-C crosslinking structure, silane coupling agent can also promote the formation of expansion charcoal layer in the polymer combustion process and the improvement of texture quality, and the flame retardant effect of conventional flame retardant is also had certain synergistic effect.For this reason; The present invention is through being combined as a whole N-substituted alkoxy hindered amine and silane coupling agent coupling; Synthetic a kind of novel multifunctional fire retarding synergist; Contain the steady and compatibilization of fire-retardant synergistic, light simultaneously, can when improving the flame-retardant polymer flame retardant properties, further improve performances such as its light is steady, mechanics.
For realizing above-mentioned purpose, the technical scheme that the present invention taked is following:
The repeated structural unit of siliceous type N-substituted alkoxy hindered amine compound of the present invention is suc as formula shown in the I:
In the formula I, X is element O or radicals R, and wherein, the structural formula of radicals R is suc as formula shown in the II:
In the formula II, R
1General formula be-HN (CH
2CH
2NH)
n(CH
2)
3-, wherein, n is 0 ~ 2; R
2Be that general formula is-C
mH
2m+1Alkyl, wherein, m is 1 ~ 8; R
3Be that general formula is-C
kH
2k-alkyl, wherein, k is 1 ~ 6; R
4, R
5Be that general formula is-C
iH
2i+1Alkyl or general formula be-C
tH
2tNaphthenic base, wherein, i is 1 ~ 8, t is 1 ~ 8.
The preparation method of the siliceous type N-substituted alkoxy of the present invention hindered amine compound comprises the steps:
(1) will have suc as formula first compound shown in the III and cyanuric chloride in first organic solvent and under the effect of acid binding agent, and carry out a substitution reaction of the triazine chlorine in ring atom of cyanuric chloride, the temperature of this substitution reaction is-10 ~ 10 ℃; Wherein, the mol ratio of first compound and cyanuric chloride is 1:4 ~ 4:1, and the mol ratio of said first compound and acid binding agent is 1:5 ~ 5:1;
In the formula III, R
2Be that general formula is-C
mH
2m+1Alkyl, wherein, m is 1 ~ 8; R
3Be that general formula is-C
kH
2k-alkyl, wherein, k is 1 ~ 6; R
4, R
5Be that general formula is-C
iH
2i+1Alkyl or general formula be-C
tH
2tNaphthenic base, wherein, i is 1 ~ 8, t is 1 ~ 8;
(2) when the pH of the reaction solution of a said substitution reaction is 6 ~ 7; Its reaction system is warming up to 30 ~ 70 ℃; And drip said acid binding agent and aminosilane, and carry out two substitution reactions of the triazine chlorine in ring atom of the resulting product of a substitution reaction, the generating structure formula is also separated this intermediate product suc as formula the intermediate product shown in the IV from its reaction system; Wherein, the aminosilane that is dripped in this step and the mol ratio of acid binding agent are 1:4 ~ 4:1.
In the formula IV, R
2Be that general formula is-C
mH
2m+1Alkyl, wherein, m is 1 ~ 8; R
3Be that general formula is-C
kH
2k-alkyl, wherein, k is 1 ~ 6; R
4, R
5Be that general formula is-C
iH
2i+1Alkyl or general formula be-C
tH
2tNaphthenic base, wherein, i is 1 ~ 8, t is 1 ~ 8; R
6General formula be-HN (CH
2CH
2NH)
n(CH
2)
3Si (OH)
3, wherein, n is 0 ~ 2;
The general formula of said aminosilane is H
2N (CH
2CH
2NH)
q(CH
2)
3Si (OCH
3)
3Or H
2N (CH
2CH
2NH)
q(CH
2)
3Si (OH)
3, wherein, q is 0 ~ 2;
(3) isolated intermediate product and said aminosilane are carried out three substitution reactions of the triazine chlorine in ring atom of said intermediate product in second organic solvent and under the effect of said acid binding agent; In this three substitution reaction; Temperature of reaction is 70 ~ 110 ℃, and the mol ratio of aminosilane and acid binding agent is at 1:4 ~ 4:1;
(4) when the pH of the reaction solution of three substitution reactions is 8 ~ 9, drip basic soln and carry out gel reaction, generate suc as formula the final product shown in the I; Wherein, said basic soln is ammoniacal liquor, bicarbonate aqueous solution or the metal hydroxides aqueous solution.
Further, the mol ratio of first compound according to the invention and cyanuric chloride is 1:1 ~ 1:2, and the mol ratio of said first compound and acid binding agent is 1:3 ~ 2:1.
Further, first organic solvent according to the invention is THF or organic solvent of ketone.
Further, the present invention is acetone or butanone as the organic solvent of ketone of said first organic solvent.
Further, second organic solvent according to the invention is dioxane or methyl-sulphoxide.
Further, acid binding agent according to the invention is bicarbonate aqueous solution, the metal hydroxides aqueous solution or organic amine.
Further, acid binding agent according to the invention is aqueous sodium hydroxide solution, sodium bicarbonate aqueous solution, triethylamine or N, N-di-isopropyl ethane.
Further, basic soln according to the invention is saturated ammoniacal liquor, sodium hydroxide solution or saturated aqueous solution of sodium bicarbonate.
Compared with prior art; The invention has the beneficial effects as follows: the gel reaction of the chlorine substitution reaction that is easy to control through cyanuric chloride and the energy-conserving and environment-protective of silane coupling agent; N-substituted alkoxy hindered amine and silane coupling agent coupling agent are combined as a whole; Synthetic a kind of novel multifunctional fire retarding synergist makes that it contains fire-retardant synergistic simultaneously, light is steady and compatibilization, can when improving the flame-retardant polymer flame retardant properties, further improve performances such as its light is steady, mechanics.This compound method adopts the silane gel reaction; Contain a large amount of the structure of hindered amine in the molecule of the gel that generates; Can form crosslinking structure at polymeric surface layer behind a large amount of macromole high energy radicals that in catching the polymer combustion degradation process, produce; Thereby significantly improve the structure and the quality of the charcoal layer that polymer surfaces takes blocking effect, significantly promote the flame retarding efficiency of phosphorus system, expansion type flame-retardant polymer.In addition, the silane gel reaction is simple to operate, and product is easily separated, for overcoming small molecules N-substituted alkoxy hindered amine is prone to aspects such as migration, volatile and extracting in polymer materials deficiency a kind of energy-conserving and environment-protective and efficient ways is provided.
Embodiment
Below in conjunction with instance the present invention is further specified.
Embodiment 1:
7.376g (0.04mol) cyanuric chloride that will be dissolved in 80ml acetone joins in the 500m1 reaction kettle that TM, magneton (magnetic stirring apparatus) are housed; The low temperature thermostat bath temperature control also fully stirs, and makes reactant homodisperse and keep the temperature of reaction system to be-10 ℃.With 7.572g (0.01mol) structural formula suc as formula first compound (wherein, the R shown in the III
2Be alkyl-C
2H
5, R
3Be alkyl-C
2H
4-, R
4Be alkyl-CH
4, R
5Be naphthenic base-C
3H
6) and 8.70ml acid binding agent N; N-sec.-propyl ethane (0.05mol) is dissolved in the 30ml acetone, in reaction kettle, dropwise drips the control rate of addition with microsyringe; Temperature of reaction is controlled under-10 ℃, carries out a substitution reaction of the triazine chlorine in ring atom on the cyanuric chloride.After dripping end, continue reaction 5h at-10 ℃ of following low temperature, this moment, the pH of reaction solution was 6.0.After the solution in the reaction kettle is poured into the 250ml there-necked flask and is moved in the heat collecting type magnetic stirring apparatus; Bring up to 50 ℃ to the temperature of reaction system gradually; Drip in the there-necked flask with microsyringe and to be dissolved with 1.65ml 3-aminopropyl ortho-siliformic acid (0.015mol) and 2.61ml acid binding agent N; The acetone soln 20ml of N-di-isopropyl ethane (0.015mol), thus carry out two substitution reactions of the triazine chlorine in ring atom of the resulting product of a substitution reaction.After dropwising, continue reaction 3h down at 50 ℃, generate intermediate product, the pH that records reaction system this moment is 7.0.Afterwards; Steaming desolventizes acetone on Rotary Evaporators, separates the intermediate product that obtains being yellow thick liquid state, puts it into and dries the back taking-up of spending the night in the vacuum drying oven; Porphyrize is Powdered back with acetone (1:1; Volume ratio) wash 3 times, put into vacuum drying oven vacuum-drying 24h once more after removing unreacted organic molecule, porphyrize is the resulting intermediate product in Powdered back and is faint yellow powdery.The productive rate of intermediate product is 97.56%.
The structural formula of intermediate product is suc as formula shown in the IV, wherein, and the R in the formula IV
2Be alkyl-C
2H
5, R
3Be alkyl-C
2H
4-, R
4Be alkyl-CH
4, R
5Be naphthenic base-C
3H
6, R
6For-HN (CH
2)
3Si (OH)
3(R
6Structural formula specifically suc as formula shown in the V).IR Characterization result to middle product is: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
The 0.005mol intermediate product is joined in the 50ml dioxane solution (back is handled in the deoxygenation that dewaters distillation); Bring up to 90 ℃ to temperature of reaction gradually; Drip in the there-necked flask with microsyringe simultaneously and be dissolved with 1.10ml 3-aminopropyl ortho-siliformic acid (0.01mol) and 1.74ml acid binding agent N; The acetone soln 10ml of N-di-isopropyl ethane (0.01mol) carries out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heating up keeps back flow reaction 3h, and the pH that records reaction system this moment is 8.0.Then, the 10ml saturated aqueous solution of sodium bicarbonate is dropwise splashed in the there-necked flask, carry out gel reaction with microsyringe.After dropwising, continue to keep back flow reaction 1h, the pH that records reaction system this moment is 9.0.Finish reaction, filter, washing; Vacuum drying; The structural formula that obtains its repeating unit is suc as formula (wherein, the X in the formula I is a structural formula suc as formula the siliceous type N-substituted alkoxy of the yellow powdery final product hindered amine compound of the radicals R shown in the VI=a), and productive rate is 72.46% shown in the I.IR Characterization result to this final product is following:
FTIR(KBr,cm
-1):1261.7(Si-C,wagging),1026.2-1197.8(Si-O,stretching?vibration),802.8(Si-C)。
In Vestolen PP 7052 (PP), add the siliceous type N-substituted alkoxy of synthetic final product hindered amine compound (Si-NORs), oxidation inhibitor B215 and compatilizer PP-g-MAH in conventional expanded type fire retardant (IFR), the present embodiment; Wherein, IFR comprises ammonium polyphosphate (APP), tetramethylolmethane (PER) and trimeric cyanamide (MEL), and three's mass ratio is APP:PER:MEL=2:2:1.According to the prescription of table 1, with the material of table 1 join carry out uniform mixing in the high speed mixer and on twin screw extruder, extrude, granulation, on vulcanizing press, be hot pressed into the sample that needs then, carry out fire-retardant and uvioresistant performance test.
Table 1
Flame retardant properties test: adopt limiting oxygen index(LOI) test (LOI) and vertical combustion test (UL-94 grade mensuration) to characterize.
Uvioresistant performance: expansion type flame-retarding PP sample is all handled through UV-irradiation in UV-light accelerated deterioration case.The ultraviolet lamp tube ultraviolet wavelength mainly concentrates on about the 313nm place in the ageing oven, and power of lamp tube is 40W, 0.8W/m
2The temperature inside the box maintains 60 ℃.Expansion type flame-retarding PP sample takes out at a distance from for some time and surveys yellowness index and mechanical property.
Table 2 is the influence of Si-NORs (R=a) to the flame retardant effect of the fire-retardant PP of conventional expanded type.
Table 2Si-NORs (R=a) is to the influence of the fire-retardant PP flame retardant effect of conventional expanded type
Table 3 is the influence of Si-NORs (R=a) to the fire-retardant PP uvioresistant performance of conventional expanded type (yellowness index).
Table 3Si-NORs (R=a) is to the influence of the fire-retardant PP yellowness index of conventional expanded type
Table 4 is the influence of Si-NORs (R=a) to the fire-retardant PP uvioresistant performance influence of conventional expanded type (mechanical property).
Table 4Si-NORs (R=a) is to the influence of the fire-retardant PP mechanical property of conventional expanded type
Embodiment 2:
3.688g (0.02mol) cyanuric chloride that will be dissolved in the 80ml butanone joins in the 500m1 reaction kettle that TM, magneton (magnetic stirring apparatus) are housed; The low temperature thermostat bath temperature control also fully stirs, and makes reactant homodisperse and to keep the temperature of reaction system be 10 ℃.With 7.572g (0.01mol) structural formula suc as formula first compound (wherein, the R shown in the III
2Be alkyl-C
2H
5, R
3Be alkyl-C
2H
4-, R
4Be alkyl-CH
4, R
5Be naphthenic base-C
3H
6) and the 15ml acid binding agent NaOH aqueous solution (2.0mol/L) be dissolved in the 30ml butanone; In reaction kettle, dropwise drip simultaneously with microsyringe; The control rate of addition, temperature of reaction is controlled under 10 ℃, carries out a substitution reaction of the triazine chlorine in ring atom on the cyanuric chloride.After dripping end, continue reaction 2h at 10 ℃ of following low temperature, this moment, the pH of reaction solution was 6.5.After the solution in the reaction kettle is poured into the 250ml there-necked flask and is moved in the heat collecting type magnetic stirring apparatus; Bring up to 50 ℃ to the temperature of reaction system gradually; Drip simultaneously in the there-necked flask with microsyringe and to be dissolved with the butanone solution 20ml and the 5ml acid binding agent NaOH aqueous solution (3.0mol/L) of 1.65ml 3-aminopropyl ortho-siliformic acid (0.015mol), thereby carry out two substitution reactions of the triazine chlorine in ring atom of the resulting product of a substitution reaction.After dropwising, continue reaction 3h down at 50 ℃, generate intermediate product, the pH that records reaction system this moment is 7.5, and reaction finishes.Afterwards; Steaming desolventizes butanone on Rotary Evaporators, separates the intermediate product that obtains being yellow thick liquid state, puts it into and dries the back taking-up of spending the night in the vacuum drying oven; Porphyrize is Powdered back with butanone/water (1:1; Volume ratio) wash 3 times, put into vacuum drying oven vacuum-drying 24h once more after removing unreacted organic molecule, porphyrize is the resultant intermediate product in Powdered back and is faint yellow powdery.The productive rate of intermediate product is 83.25%.
The structural formula of intermediate product is suc as formula shown in the IV, wherein, and R
2Be alkyl-C
2H
5, R
3Be alkyl-C
2H
4-, R
4Be alkyl-CH
4, R
5Be naphthenic base-C
3H
6, R
6For-HN (CH
2)
3Si (OH)
3, specifically suc as formula shown in the V).IR Characterization result to middle product is: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
The 0.005mol intermediate product is joined in the 50ml dioxane solution (back is handled in the deoxygenation that dewaters distillation); Bring up to 90 ℃ to temperature of reaction gradually; In there-necked flask, drip the butanone solution 10ml and the 5ml acid binding agent NaOH aqueous solution (2.0mol/L) that is dissolved with 1.10ml 3-aminopropyl ortho-siliformic acid (0.01mol) with microsyringe simultaneously simultaneously, carry out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heating up keeps back flow reaction 3h, and the pH that records reaction system this moment is 8.0.Afterwards, with microsyringe the 10ml saturated aqueous solution of sodium bicarbonate is dropwise splashed into and carry out gel reaction in the there-necked flask.After dropwising, continue to keep back flow reaction 1h, the pH that records reaction system is 9.0.Finish reaction, filter, washing; Vacuum drying; The structural formula that obtains its repeating unit is suc as formula (wherein, the X in the formula I is a structural formula suc as formula the siliceous type N-substituted alkoxy of the yellow powdery final product hindered amine compound of the radicals R shown in the VI=a), and productive rate is 65.21% shown in the I.IR Characterization result to this final product is following:
FTIR(KBr,cm
-1):1261.7(Si-C,wagging),1026.2-1197.8(Si-O,stretching?vibration),802.8(Si-C)。
In PP, add synthetic final product Si-NORs, oxidation inhibitor B215 and compatilizer PP-g-MAH in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and three's mass ratio is APP:PER:MEL=2:2:1.According to the prescription of table 1, with the material of table 1 join carry out uniform mixing in the high speed mixer and on twin screw extruder, extrude, granulation, on vulcanizing press, be hot pressed into the sample that needs then, carry out fire-retardant and uvioresistant performance test.Its result is shown in table 5-7.
Table 5Si-NORs (R=a) is to the influence of the fire-retardant PP flame retardant effect of conventional expanded type
Table 6Si-NORs (R=a) is to the influence of the fire-retardant PP yellowness index of conventional expanded type
Table 7Si-NORs (R=a) is to the influence of the fire-retardant PP mechanical property of conventional expanded type
Embodiment 3:
1.844g (0.01mol) cyanuric chloride that will be dissolved in 80ml acetone joins in the 500m1 reaction kettle that TM, magneton (magnetic stirring apparatus) are housed; The low temperature thermostat bath temperature control also fully stirs, and makes reactant homodisperse and to keep the temperature of reaction system be 5 ℃.With 7.572g (0.01mol) structural formula suc as formula first compound (wherein, the R shown in the III
2Be alkyl-C
2H
5, R
3Be alkyl-C
2H
4-, R
4Be alkyl-CH
4, R
5Be naphthenic base-C
3H
6) and 0.870ml acid binding agent N; N-sec.-propyl ethane (0.005mol) is dissolved in the 30ml acetone, in reaction kettle, dropwise drips the control rate of addition with microsyringe; Temperature of reaction is controlled under 5 ℃, carries out a substitution reaction of the triazine chlorine in ring atom on the cyanuric chloride.After dripping end, continue reaction 3h at 5 ℃ of following low temperature, this moment, the pH of reaction solution was 6.5.After the solution in the reaction kettle is poured into the 250ml there-necked flask and is moved in the heat collecting type magnetic stirring apparatus; Bring up to 50 ℃ to the temperature of reaction system gradually; Drip in the there-necked flask with microsyringe and to be dissolved with 2.67ml 3-aminopropyl trimethoxysilane (0.015mol) and 2.61ml acid binding agent N; The acetone soln 20ml of N-di-isopropyl ethane (0.015mol), thus carry out two substitution reactions of the triazine chlorine in ring atom of the resulting product of a substitution reaction.After dropwising, continue reaction 3h down at 50 ℃, generate intermediate product, the pH that records reaction system this moment is 7.5, and reaction finishes.Afterwards; Steaming desolventizes acetone on Rotary Evaporators, separates the intermediate product that obtains being yellow thick liquid state, puts it into and dries the back taking-up of spending the night in the vacuum drying oven; Porphyrize is Powdered back with acetone (1:1; Volume ratio) wash 3 times, put into vacuum drying oven vacuum-drying 24h once more after removing unreacted organic molecule, porphyrize is the resultant intermediate product in Powdered back and is faint yellow powdery.The productive rate of intermediate product is 98.26%.
The structural formula of intermediate product is suc as formula shown in the IV, wherein, and R
2Be alkyl-C
2H
5, R
3Be alkyl-C
2H
4-, R
4Be alkyl-CH
4, R
5Be naphthenic base-C
3H
6, R
6For-HN (CH
2)
3Si (OH)
3, specifically suc as formula shown in the V.IR Characterization result to middle product is: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
The 0.005mol intermediate product is joined in the 50ml dimethyl sulfoxide solution (back is handled in the deoxygenation that dewaters distillation); Bring up to 90 ℃ to temperature of reaction gradually; Drip in the there-necked flask with microsyringe simultaneously and be dissolved with 1.78ml 3-aminopropyl trimethoxysilane (0.01mol) and 1.74ml acid binding agent N; The acetone soln 10ml of N-di-isopropyl ethane (0.01mol) carries out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heating up keeps back flow reaction 3h, and the pH that records reaction system this moment is 8.5.Then, with microsyringe the 10ml saturated ammonia aqueous solution is dropwise splashed into and carry out gel reaction in the there-necked flask.After dropwising, continue to keep back flow reaction 1h, the pH that records reaction system is 9.0.Finish reaction, filter, washing; Vacuum drying; The structural formula that obtains its repeating unit is suc as formula (wherein, the X in the formula I is a structural formula suc as formula the siliceous type N-substituted alkoxy of the yellow powdery final product hindered amine compound of the radicals R shown in the VI=a), and productive rate is 75.98% shown in the I.IR Characterization result to this final product is following:
FTIR(KBr,cm
-1):1261.7(Si-C,wagging),1026.2-1197.8(Si-O,stretching?vibration),802.8(Si-C)。
In PP, add synthetic final product Si-NORs, oxidation inhibitor B215 and compatilizer PP-g-MAH in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and three's mass ratio is APP:PER:MEL=2:2:1.According to the prescription of table 1, with the material of table 1 join carry out uniform mixing in the high speed mixer and on twin screw extruder, extrude, granulation, on vulcanizing press, be hot pressed into the sample that needs then, carry out fire-retardant and uvioresistant performance test.Its result is shown in table 8-10.
Table 8Si-NORs (R=a) is to the influence of the fire-retardant PP flame retardant effect of conventional expanded type
Table 9Si-NORs (R=a) is to the influence of the fire-retardant PP yellowness index of conventional expanded type
Embodiment 4:
0.461g (0.0025mol) cyanuric chloride that will be dissolved in the 80ml butanone joins in the 500m1 reaction kettle that TM, magneton (magnetic stirring apparatus) are housed; The low temperature thermostat bath temperature control also fully stirs, and makes reactant homodisperse and to keep the temperature of reaction system be 5 ℃.With 7.572g (0.01mol) structural formula suc as formula first compound (wherein, the R shown in the III
2Be alkyl-C
2H
5, R
3Be alkyl-C
2H
4-, R
4Be alkyl-CH
4, R
5Be naphthenic base-C
3H
6) and the 0.67ml acid binding agent NaOH aqueous solution (3.0mol/L) be dissolved in the 30ml butanone; In reaction kettle, dropwise drip simultaneously with microsyringe; The control rate of addition, temperature of reaction is controlled under 5 ℃, carries out a substitution reaction of the triazine chlorine in ring atom on the cyanuric chloride.After dripping end, continue reaction 3h at 5 ℃ of following low temperature, this moment, the pH of reaction solution was 7.0.After the solution in the reaction kettle is poured into the 250ml there-necked flask and is moved in the heat collecting type magnetic stirring apparatus; Bring up to 50 ℃ to the temperature of reaction system gradually; Drip simultaneously in the there-necked flask with microsyringe and to be dissolved with the butanone solution 20ml and the 7.5ml acid binding agent NaOH aqueous solution (2.0mol/L) of 2.67ml 3-aminopropyl trimethoxysilane (0.015mol), thereby carry out two substitution reactions of the triazine chlorine in ring atom of the resulting product of a substitution reaction.After dropwising, continue reaction 3h down at 50 ℃, generate intermediate product, the pH that records reaction system this moment is 7.5, and reaction finishes.Afterwards; Steaming desolventizes butanone on Rotary Evaporators, separates the intermediate product that obtains being yellow thick liquid state, puts it into and dries the back taking-up of spending the night in the vacuum drying oven; Porphyrize is Powdered back with butanone/water (1:1; Volume ratio) wash 3 times, put into vacuum drying oven vacuum-drying 24h once more after removing unreacted organic molecule, porphyrize is the resultant intermediate product in Powdered back and is faint yellow powdery.The productive rate of intermediate product is 66.26%.
The structural formula of intermediate product is suc as formula shown in the IV, wherein, and R
2Be alkyl-C
2H
5, R
3Be alkyl-C
2H
4-, R
4Be alkyl-CH
4, R
5Be naphthenic base-C
3H
6, R
6For-HN (CH
2)
3Si (OH)
3, specifically suc as formula shown in the V.IR Characterization result to middle product is: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
The 0.005mol intermediate product is joined in the 50ml dimethyl sulfoxide solution (back is handled in the deoxygenation that dewaters distillation); Bring up to 90 ℃ to temperature of reaction gradually; In there-necked flask, drip the butanone solution 10ml and the 5ml acid binding agent NaOH aqueous solution (2.0mol/L) that is dissolved with 1.78ml 3-aminopropyl trimethoxysilane (0.01mol) with microsyringe simultaneously simultaneously, carry out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heating up keeps back flow reaction 3h, and the pH that records reaction system this moment is 8.5.Then, with microsyringe the 10ml saturated ammonia aqueous solution is dropwise splashed into and carry out gel reaction in the there-necked flask.After dropwising, continue to keep back flow reaction 1h, the pH that records reaction system is 9.0.Finish reaction, filter, washing; Vacuum drying; The structural formula that obtains its repeating unit is suc as formula (wherein, the X in the formula I is a structural formula suc as formula the siliceous type N-substituted alkoxy of the yellow powdery final product hindered amine compound of the radicals R shown in the VI=a), and productive rate is 72.35% shown in the I.IR Characterization result to this final product is following:
FTIR(KBr,cm
-1):1261.7(Si-C,wagging),1026.2-1197.8(Si-O,stretching?vibration),802.8(Si-C)。
In PP, add synthetic final product Si-NORs, oxidation inhibitor B215 and compatilizer PP-g-MAH in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and three's mass ratio is APP:PER:MEL=2:2:1.According to the prescription of table 1, with the material of table 1 join carry out uniform mixing in the high speed mixer and on twin screw extruder, extrude, granulation, on vulcanizing press, be hot pressed into the sample that needs then, carry out fire-retardant and uvioresistant performance test.Its result is shown in table 11-13.
Table 11Si-NORs (R=a) is to the influence of the fire-retardant PP flame retardant effect of conventional expanded type
Table 12Si-NORs (R=a) is to the influence of the fire-retardant PP yellowness index of conventional expanded type
Table 13Si-NORs (R=a) is to the influence of the fire-retardant PP mechanical property of conventional expanded type
Embodiment 5:
3.688g (0.02mol) cyanuric chloride that will be dissolved in the 80ml THF joins in the 500m1 reaction kettle that TM, magneton (magnetic stirring apparatus) are housed; The low temperature thermostat bath temperature control also fully stirs, and makes reactant homodisperse and to keep the temperature of reaction system be 5 ℃.With 7.572g (0.01mol) structural formula suc as formula first compound (wherein, the R shown in the III
2Be alkyl-C
4H
9, R
3Be alkyl-C
3H
6-, R
4Be alkyl-C
6H
13, R
5Be naphthenic base-C
6H
12) and 4.18ml acid binding agent triethylamine (0.03mol) be dissolved in the 30ml THF; Dropwise drip in reaction kettle with microsyringe; The control rate of addition, temperature of reaction is controlled under 5 ℃, carries out a substitution reaction of the triazine chlorine in ring atom on the cyanuric chloride.After dripping end, continue reaction 3h at 5 ℃ of following low temperature, this moment, the pH of reaction solution was 7.0.After the solution in the reaction kettle is poured into the 250ml there-necked flask and is moved in the heat collecting type magnetic stirring apparatus; Bring up to 30 ℃ to the temperature of reaction system gradually; Drip in the there-necked flask with microsyringe and to be dissolved with the tetrahydrofuran solution 20ml of 3.21ml3-(2-aminoethylamino) propyl trimethoxy silicane (0.015mol) and acid binding agent 11.16ml triethylamine (0.06mol), thereby carry out two substitution reactions of the triazine chlorine in ring atom of the resulting product of a substitution reaction.After dropwising, continue reaction 5h down at 30 ℃, generate intermediate product, the pH that records reaction system this moment is 8.0, and reaction finishes.Afterwards; Steaming desolventizes THF on Rotary Evaporators, separates the intermediate product that obtains being yellow thick liquid state, puts it into and dries the back taking-up of spending the night in the vacuum drying oven; Porphyrize is Powdered back with THF/water (1:1; Volume ratio) wash 3 times, put into vacuum drying oven vacuum-drying 24h once more after removing unreacted organic molecule, porphyrize is the resultant intermediate product in Powdered back and is faint yellow powdery.The productive rate of intermediate product is 98.52%.
The structural formula of intermediate product is suc as formula shown in the IV, wherein, and R
2Be alkyl-C
4H
9, R
3Be alkyl-C
3H
6-, R
4Be alkyl-C
6H
13, R
5Be naphthenic base-C
6H
12, R
6For-HN (CH
2CH
2NH) (CH
2)
3Si (OH)
3, specifically suc as formula shown in the VI.IR Characterization result to middle product is: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
The 0.005mol intermediate product is joined in the 50ml dioxane solution (back is handled in the deoxygenation that dewaters distillation); Bring up to 90 ℃ to temperature of reaction gradually; In there-necked flask, drip the tetrahydrofuran solution 10ml that is dissolved with 2.14ml 3-(2-aminoethylamino) propyl trimethoxy silicane (0.01mol) and 1.40ml acid binding agent triethylamine (0.01mol) with microsyringe simultaneously, carry out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heating up keeps back flow reaction 3h, and the pH that records reaction system this moment is 8.5.Then, with microsyringe the saturated NaOH aqueous solution of 10ml is dropwise splashed into and carry out gel reaction in the there-necked flask.After dropwising, continue to keep back flow reaction 1h, the pH that records reaction system is 9.0.Finish reaction, filter, washing; Vacuum drying; The structural formula that obtains its repeating unit is suc as formula (wherein, the X in the formula I is a structural formula suc as formula the siliceous type N-substituted alkoxy of the yellow powdery final product hindered amine compound of the radicals R shown in the VII=b), and productive rate is 76.12% shown in the I.IR Characterization result to this final product is following:
FTIR(KBr,cm
-1):1261.7(Si-C,wagging),1026.2-1197.8(Si-O,stretching?vibration),802.8(Si-C)。
In PP, add synthetic final product Si-NORs, oxidation inhibitor B215 and compatilizer PP-g-MAH in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and three's mass ratio is APP:PER:MEL=2:2:1.According to the prescription of table 1, with the material of table 1 join carry out uniform mixing in the high speed mixer and on twin screw extruder, extrude, granulation, on vulcanizing press, be hot pressed into the sample that needs then, carry out fire-retardant and uvioresistant performance test.Its result is shown in table 14-16.
Table 14Si-NORs (R=b) is to the influence of the fire-retardant PP flame retardant effect of conventional expanded type
Table 15Si-NORs (R=b) is to the influence of the fire-retardant PP yellowness index of conventional expanded type
Table 16Si-NORs (R=b) is to the influence of the fire-retardant PP mechanical property of conventional expanded type
Embodiment 6:
3.688g (0.02mol) cyanuric chloride that will be dissolved in the 80ml THF joins in the 500m1 reaction kettle that TM, magneton (magnetic stirring apparatus) are housed; The low temperature thermostat bath temperature control also fully stirs, and makes reactant homodisperse and to keep the temperature of reaction system be 5 ℃.With 7.572g (0.01mol) structural formula suc as formula first compound (wherein, the R shown in the III
2Be alkyl-C
4H
9, R
3Be alkyl-C
3H
6-, R
4Be alkyl-C
6H
13, R
5Be naphthenic base-C
6H
12) and 10ml acid binding agent NaHCO
3The aqueous solution (3.0mol/L) is dissolved in the 30ml THF, in reaction kettle, dropwise drips simultaneously with microsyringe, and the control rate of addition, temperature of reaction is controlled under 5 ℃, carries out a substitution reaction of the triazine chlorine in ring atom on the cyanuric chloride.After dripping end, continue reaction 3h at 5 ℃ of following low temperature, this moment, the pH of reaction solution was 7.0.After the solution in the reaction kettle is poured into the 250ml there-necked flask and is moved in the heat collecting type magnetic stirring apparatus; Bring up to 70 ℃ to the temperature of reaction system gradually, in there-necked flask, drip tetrahydrofuran solution 20ml and the 1.25ml acid binding agent NaHCO that is dissolved with 3.21ml 3-(2-aminoethylamino) propyl trimethoxy silicane (0.015mol) simultaneously with microsyringe
3The aqueous solution (3.0mol/L), thus carry out two substitution reactions of the triazine chlorine in ring atom of the resulting product of a substitution reaction.After dropwising, continue reaction 1h down at 70 ℃, generate intermediate product, the pH that records reaction system this moment is 8.0, and reaction finishes.Afterwards; Steaming desolventizes THF on Rotary Evaporators, separates the intermediate product that obtains being yellow thick liquid state, puts it into and dries the back taking-up of spending the night in the vacuum drying oven; Porphyrize is Powdered back with THF/water (1:1; Volume ratio) wash 3 times, put into vacuum drying oven vacuum-drying 24h once more after removing unreacted organic molecule, porphyrize is the resultant intermediate product in Powdered back and is faint yellow powdery.The productive rate of intermediate product is 95.43%.
The structural formula of intermediate product is suc as formula shown in the IV, wherein, and R
2Be alkyl-C
4H
9, R
3Be alkyl-C
3H
6-, R
4Be alkyl-C
6H
13, R
5Be naphthenic base-C
6H
12, R
6For-HN (CH
2CH
2NH) (CH
2)
3Si (OH)
3, specifically suc as formula shown in the VI.IR Characterization result to middle product is: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
The 0.005mol intermediate product is joined in the 50ml dimethyl sulfoxide solution (back is handled in the deoxygenation that dewaters distillation); Bring up to 90 ℃ to temperature of reaction gradually, in there-necked flask, drip tetrahydrofuran solution 10ml and the 10ml acid binding agent NaHCO that is dissolved with 2.14ml 3-(2-aminoethylamino) propyl trimethoxy silicane (0.01mol) with microsyringe simultaneously simultaneously
3The aqueous solution (1.0mol/L) carries out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heating up keeps back flow reaction 3h, and the pH that records reaction system this moment is 9.0.Then, with microsyringe the saturated NaOH aqueous solution of 10ml is dropwise splashed into and carry out gel reaction in the there-necked flask.After dropwising, continue to keep back flow reaction 1h, the pH that records reaction system is 9.5.Finish reaction, filter, washing; Vacuum drying; The structural formula that obtains its repeating unit is suc as formula (wherein, the X in the formula I is a structural formula suc as formula the siliceous type N-substituted alkoxy of the yellow powdery final product hindered amine compound of the radicals R shown in the VII=b), and productive rate is 75.24% shown in the I.IR Characterization result to this final product is following:
FTIR(KBr,cm
-1):1261.7(Si-C,wagging),1026.2-1197.8(Si-O,stretching?vibration),802.8(Si-C)。
In PP, add synthetic final product Si-NORs, oxidation inhibitor B215 and compatilizer PP-g-MAH in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and three's mass ratio is APP:PER:MEL=2:2:1.According to the prescription of table 1, with the material of table 1 join carry out uniform mixing in the high speed mixer and on twin screw extruder, extrude, granulation, on vulcanizing press, be hot pressed into the sample that needs then, carry out fire-retardant and uvioresistant performance test.Its result is shown in table 17-19.
Table 17Si-NORs (R=b) is to the influence of the fire-retardant PP flame retardant effect of conventional expanded type
Table 18Si-NORs (R=b) is to the influence of the fire-retardant PP yellowness index of conventional expanded type
Table 19Si-NORs (R=b) is to the influence of the fire-retardant PP mechanical property of conventional expanded type
Embodiment 7:
3.688g (0.02mol) cyanuric chloride that will be dissolved in 80ml acetone joins in the 500m1 reaction kettle that TM, magneton (magnetic stirring apparatus) are housed; The low temperature thermostat bath temperature control also fully stirs, and makes reactant homodisperse and to keep the temperature of reaction system be 5 ℃.With 7.572g (0.01mol) structural formula suc as formula first compound (wherein, the R shown in the III
2Be alkyl-C
8H
17, R
3Be alkyl-C
6H
12-, R
4Be naphthenic base-C
8H
16, R
5Be alkyl-C
8H
17) and 4.18ml acid binding agent triethylamine (0.03mol) be dissolved in the 30ml acetone, dropwise drip in the reaction kettle with microsyringe, the control rate of addition, temperature of reaction is controlled under 5 ℃, carries out a substitution reaction of the triazine chlorine in ring atom on the cyanuric chloride.After dripping end, continue reaction 3h at 5 ℃ of following low temperature, this moment, the pH of reaction solution was 6.5.After the solution in the reaction kettle is poured into the 250ml there-necked flask and is moved in the heat collecting type magnetic stirring apparatus; Bring up to 50 ℃ to temperature of reaction system gradually; Drip in the there-necked flask with microsyringe and to be dissolved with the acetone soln 20ml of 3.86ml diethylenetriamine base propyl trimethoxy silicane (0.015mol) and 2.79ml acid binding agent triethylamine (0.015mol), thereby carry out two substitution reactions of the triazine chlorine in ring atom of the resulting product of a substitution reaction.After dropwising, continue reaction 3h down at 50 ℃, generate intermediate product, the pH that records reaction system this moment is 7.5, and reaction finishes.Afterwards; Steaming desolventizes acetone on Rotary Evaporators, separates the intermediate product that obtains being yellow thick liquid state, puts it into and dries the back taking-up of spending the night in the vacuum drying oven; Porphyrize is Powdered back with acetone (1:1; Volume ratio) wash 3 times, put into vacuum drying oven vacuum-drying 24h once more after removing unreacted organic molecule, porphyrize is the resultant intermediate product in Powdered back and is faint yellow powdery.The productive rate of intermediate product is 99.13%.
The structural formula of intermediate product is suc as formula shown in the IV, wherein, and R
2Be alkyl-C
8H
17, R
3Be alkyl-C
6H
12-, R
4Be naphthenic base-C
8H
16, R
5Be alkyl-C
8H
17, R
6For-HN (CH
2CH
2NH)
2(CH
2)
3Si (OH)
3, specifically suc as formula shown in the VIII.IR Characterization result to middle product is: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
The 0.005mol intermediate product is joined in the 50ml dioxane solution (back is handled in the deoxygenation that dewaters distillation); Bring up to 70 ℃ to temperature of reaction gradually; In there-necked flask, drip the acetone soln 20ml that is dissolved with 2.57ml diethylenetriamine base propyl trimethoxy silicane (0.01mol) and 8.36ml acid binding agent triethylamine (0.04mol) with microsyringe simultaneously, carry out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heating up keeps back flow reaction 5h, and the pH that records reaction system this moment is 8.5.Then, with microsyringe the 5ml saturated ammonia aqueous solution is dropwise splashed into and carry out gel reaction in the there-necked flask.After dropwising, continue to keep back flow reaction 2h, the pH that records reaction system is 9.0.Finish reaction, filter, washing; Vacuum drying; The structural formula that obtains its repeating unit is suc as formula (wherein, the X in the formula I is a structural formula suc as formula the siliceous type N-substituted alkoxy of the yellow powdery final product hindered amine compound of the radicals R shown in the IX=c), and productive rate is 82.10% shown in the I.IR Characterization result to this final product is following:
FTIR(KBr,cm
-1):1261.7(Si-C,wagging),1026.2-1197.8(Si-O,stretching?vibration),802.8(Si-C)。
In PP, add synthetic final product Si-NORs, oxidation inhibitor B215 and compatilizer PP-g-MAH in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and three's mass ratio is APP:PER:MEL=2:2:1.According to the prescription of table 1, with the material of table 1 join carry out uniform mixing in the high speed mixer and on twin screw extruder, extrude, granulation, on vulcanizing press, be hot pressed into the sample that needs then, carry out fire-retardant and uvioresistant performance test.Its result is shown in table 20-22.
Table 20Si-NORs (R=c) is to the influence of the fire-retardant PP flame retardant effect of conventional expanded type
Table 21Si-NORs (R=b) is to the influence of the fire-retardant PP yellowness index of conventional expanded type
Table 22Si-NORs (R=c) is to the influence of the fire-retardant PP mechanical property of conventional expanded type
Embodiment 8:
3.688g (0.02mol) cyanuric chloride that will be dissolved in the 80ml THF joins in the 500m1 reaction kettle that TM, magneton (magnetic stirring apparatus) are housed; The low temperature thermostat bath temperature control also fully stirs, and makes reactant homodisperse and to keep the temperature of reaction system be 5 ℃.With 7.572g (0.01mol) structural formula suc as formula first compound (wherein, the R shown in the III
2Be alkyl-C
8H
17, R
3Be alkyl-C
6H
12-, R
4Be naphthenic base-C
8H
16, R
5Be alkyl-C
8H
17) and 10ml acid binding agent NaHCO
3The aqueous solution (3.0mol/L) is dissolved in the 30ml THF, in reaction kettle, dropwise drips simultaneously with microsyringe, and the control rate of addition, temperature of reaction is controlled under 5 ℃, carries out a substitution reaction of the triazine chlorine in ring atom on the cyanuric chloride.After dripping end, continue reaction 3h at 5 ℃ of following low temperature, this moment, the pH of reaction solution was 6.5.After the solution in the reaction kettle is poured into the 250ml there-necked flask and is moved in the heat collecting type magnetic stirring apparatus; Bring up to 50 ℃ to the temperature of reaction system gradually, in there-necked flask, drip tetrahydrofuran solution 20ml and the 5ml acid binding agent NaHCO that is dissolved with 3.86ml diethylenetriamine base propyl trimethoxy silicane (0.015mol) simultaneously with microsyringe
3The aqueous solution (3.0mol/L), thus carry out two substitution reactions of the triazine chlorine in ring atom of the resulting product of a substitution reaction.After dropwising, continue reaction 3h down at 50 ℃, generate intermediate product, the pH that records reaction system this moment is 7.5, and reaction finishes.Afterwards; Steaming desolventizes THF on Rotary Evaporators, separates the intermediate product that obtains being yellow thick liquid state, puts it into and dries the back taking-up of spending the night in the vacuum drying oven; Porphyrize is Powdered back with THF/water (1:1; Volume ratio) wash 3 times, put into vacuum drying oven vacuum-drying 24h once more after removing unreacted organic molecule, porphyrize is the resultant intermediate product in Powdered back and is faint yellow powdery.The productive rate of intermediate product is 99.25%.
The structural formula of intermediate product is suc as formula shown in the IV, wherein, and R
2Be alkyl-C
8H
17, R
3Be alkyl-C
6H
12-, R
4Be naphthenic base-C
8H
16, R
5Be alkyl-C
8H
17, R
6For-HN (CH
2CH
2NH)
2(CH
2)
3Si (OH)
3, specifically suc as formula shown in the VIII.IR Characterization result to middle product is: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
The 0.005mol intermediate product is joined in the 50ml dimethyl sulfoxide solution (back is handled in the deoxygenation that dewaters distillation); Bring up to 110 ℃ to temperature of reaction gradually, in there-necked flask, drip tetrahydrofuran solution 10ml and the 2.5ml acid binding agent NaHCO that is dissolved with 2.57ml diethylenetriamine base propyl trimethoxy silicane (0.01mol) with microsyringe simultaneously simultaneously
3The aqueous solution (1.0mol/L) carries out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heating up keeps back flow reaction 1h, and the pH that records reaction system this moment is 8.5.Then, with microsyringe the saturated NaOH aqueous solution of 20ml is dropwise splashed into and carry out gel reaction in the there-necked flask.After dropwising, continue to keep back flow reaction 0.5h, the pH that records reaction system is 9.5.Finish reaction, filter, washing; Vacuum drying; The structural formula that obtains its repeating unit is suc as formula (wherein, the X in the formula I is a structural formula suc as formula the siliceous type N-substituted alkoxy of the yellow powdery final product hindered amine compound of the radicals R shown in the IX=c), and productive rate is 80.23% shown in the I.IR Characterization result to this final product is following:
FTIR(KBr,cm
-1):1261.7(Si-C,wagging),1026.2-1197.8(Si-O,stretching?vibration),802.8(Si-C)。
In PP, add synthetic final product Si-NORs, oxidation inhibitor B215 and compatilizer PP-g-MAH in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and three's mass ratio is APP:PER:MEL=2:2:1.According to the prescription of table 1, with the material of table 1 join carry out uniform mixing in the high speed mixer and on twin screw extruder, extrude, granulation, on vulcanizing press, be hot pressed into the sample that needs then, carry out fire-retardant and uvioresistant performance test.Its result is shown in table 23-25.
Table 23Si-NORs (R=c) is to the influence of the fire-retardant PP flame retardant effect of conventional expanded type
Table 24Si-NORs (R=b) is to the influence of the fire-retardant PP yellowness index of conventional expanded type
Table 25Si-NORs (R=c) is to the influence of the fire-retardant PP mechanical property of conventional expanded type
Can see through above The performance test results; The N-substituted alkoxy hindered amine compound Si-NORs of different structure of the present invention has the excellent fire retardant synergistic effect, only adds LOI value and UL-94 grade that 1wt%N-substituted alkoxy hindered amine compound can increase the fire-retardant PP of conventional expanded type significantly.After adding Si-NORs, the LOI value of the fire-retardant PP of conventional expanded type all can be promoted to more than 32 from 28.The improvement of UL-94 grade aspect is more outstanding; Its UL-94 grade can the time have the molten drop phenomenon, can't bring up to through the best V-0 grade of flame retardant properties through minimum V-2 grade from burning, makes the fire-retardant PP of conventional expanded type reach the flame retardant test standard of extensive approval.This effect is come the unique texture as for Si-NORs of the present invention.In the combustion processes of PP, on the one hand, the free radical scavenger that Si-NORs produces in gas-phase decomposition can be caught the high energy radical that the PP burning produces, and disturbs the free radical reaction in the combustion processes; On the other hand, Si-NORs decomposes the Si-O-C and the Si-C crosslinking structure that produce at condensed phase can also increase the melt strength in the PP combustion processes, promotes the foaming form of expansion charcoal layer, further promotes the thermostability and obstruct effect of expansion charcoal layer.In addition; Yellowness index and Mechanics Performance Testing result by expansion type flame-retarding PP show; Than the expansion type flame-retarding PP that does not add N-substituted alkoxy hindered amine compound, behind the N-substituted alkoxy hindered amine compound of interpolation 1wt%, yellowing and the mechanical property deterioration degree of expansion type flame-retarding PP under the ultraviolet radiation condition obtains improvement in various degree; And along with the increase of ultraviolet radiation time, its yellowing and mechanical property deterioration degree weaken more obviously.Therefore; Synthetic N-substituted alkoxy hindered amine compound of the present invention contains fire-retardant synergistic, light is steady and compatibilization; Can when improving traditional flame-retardant polymer flame retardant properties, further improve performances such as its light is steady, mechanics, be a kind of novel multifunctional fire retarding synergist.
Claims (9)
1. siliceous type N-substituted alkoxy hindered amine compound is characterized in that the structure of its repeating unit is suc as formula shown in the I:
In the formula I, X is element O or radicals R, and wherein, the structural formula of radicals R is suc as formula shown in the II:
In the formula II, R
1General formula be-HN (CH
2CH
2NH)
n(CH
2)
3-, wherein, n is 0 ~ 2; R
2Be that general formula is-C
mH
2m+1Alkyl, wherein, m is 1 ~ 8; R
3Be that general formula is-C
kH
2k-alkyl, wherein, k is 1 ~ 6; R
4, R
5Be that general formula is-C
iH
2i+1Alkyl or general formula be-C
tH
2tNaphthenic base, wherein, i is 1 ~ 8, t is 1 ~ 8.
2. the preparation method of the compound of a claim 1 is characterized in that, comprises the steps:
(1) will have suc as formula first compound shown in the III and cyanuric chloride in first organic solvent and under the effect of acid binding agent, and carry out a substitution reaction of the triazine chlorine in ring atom of cyanuric chloride, the temperature of this substitution reaction is-10 ~ 10 ℃; Wherein, the mol ratio of first compound and cyanuric chloride is 1:4 ~ 4:1, and the mol ratio of said first compound and acid binding agent is 1:5 ~ 5:1;
In the formula III, R
2Be that general formula is-C
mH
2m+1Alkyl, wherein, m is 1 ~ 8; R
3Be that general formula is-C
kH
2k-alkyl, wherein, k is 1 ~ 6; R
4, R
5Be that general formula is-C
iH
2i+1Alkyl or general formula be-C
tH
2tNaphthenic base, wherein, i is 1 ~ 8, t is 1 ~ 8;
(2) when the pH of the reaction solution of a said substitution reaction is 6 ~ 7; Its reaction system is warming up to 30 ~ 70 ℃; And drip said acid binding agent and aminosilane by the mol ratio of 1:4 ~ 4:1, carry out two substitution reactions of the triazine chlorine in ring atom of the resulting product of a substitution reaction, when the pH that proceeds to reaction solution when two substitution reactions is 7 ~ 8; Generation is separated said intermediate product suc as formula the intermediate product shown in the IV then from its reaction system;
In the formula IV, R
2Be that general formula is-C
mH
2m+1Alkyl, wherein, m is 1 ~ 8; R
3Be that general formula is-C
kH
2k-alkyl, wherein, k is 1 ~ 6; R
4, R
5Be that general formula is-C
iH
2i+1Alkyl or general formula be-C
tH
2tNaphthenic base, wherein, i is 1 ~ 8, t is 1 ~ 8; R
6General formula be-HN (CH
2CH
2NH)
n(CH
2)
3Si (OH)
3, wherein, n is 0 ~ 2;
The general formula of said aminosilane is H
2N (CH
2CH
2NH)
q(CH
2)
3Si (OCH
3)
3Or H
2N (CH
2CH
2NH)
q(CH
2)
3Si (OH)
3, wherein, q is 0 ~ 2;
(3) isolated intermediate product and said aminosilane are carried out three substitution reactions of the triazine chlorine in ring atom of said intermediate product in second organic solvent and under the effect of said acid binding agent; In this three substitution reaction; Temperature of reaction is 70 ~ 110 ℃, and the mol ratio of aminosilane and acid binding agent is at 1:4 ~ 4:1;
(4) when the pH of the reaction solution of three substitution reactions is 8 ~ 9, drip basic soln and carry out gel reaction, generate suc as formula the final product shown in the I; Wherein, said basic soln is ammoniacal liquor, bicarbonate aqueous solution or the metal hydroxides aqueous solution.
3. preparation method according to claim 2 is characterized in that: the mol ratio of said first compound and cyanuric chloride is 1:1 ~ 1:2, and the mol ratio of said first compound and acid binding agent is 1:3 ~ 2:1.
4. preparation method according to claim 2 is characterized in that: said first organic solvent is THF or organic solvent of ketone.
5. preparation method according to claim 4 is characterized in that: the organic solvent of ketone as said first organic solvent is acetone or butanone.
6. preparation method according to claim 2 is characterized in that: said second organic solvent is dioxane or methyl-sulphoxide.
7. preparation method according to claim 2 is characterized in that: said acid binding agent is bicarbonate aqueous solution, the metal hydroxides aqueous solution or organic amine.
8. preparation method according to claim 7 is characterized in that: said acid binding agent is aqueous sodium hydroxide solution, sodium bicarbonate aqueous solution, triethylamine or N, N-di-isopropyl ethane.
9. preparation method according to claim 2 is characterized in that: said basic soln is saturated ammoniacal liquor, sodium hydroxide solution or saturated aqueous solution of sodium bicarbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN110776635A (en) * | 2019-10-12 | 2020-02-11 | 华南理工大学 | Single-component intumescent flame retardant with free radical quenching function and preparation method and application thereof |
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| GB1466992A (en) * | 1973-02-21 | 1977-03-16 | Siemens Ag | Triazine derivatives |
| US5561179A (en) * | 1994-11-30 | 1996-10-01 | Ciba-Geigy Corporation | Piperidine compounds containing silane groups as stabilizers for organic materials |
| CN1616468A (en) * | 2003-06-30 | 2005-05-18 | 三星电子株式会社 | Multi-functional cyclic siloxane compound, siloxane-based polymer prepared from the compound and process for preparing dielectric film by using the polymer |
| CN101024632A (en) * | 2007-03-23 | 2007-08-29 | 东北林业大学 | Triazine series oligomer and its synthesizing method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1466992A (en) * | 1973-02-21 | 1977-03-16 | Siemens Ag | Triazine derivatives |
| US5561179A (en) * | 1994-11-30 | 1996-10-01 | Ciba-Geigy Corporation | Piperidine compounds containing silane groups as stabilizers for organic materials |
| CN1616468A (en) * | 2003-06-30 | 2005-05-18 | 三星电子株式会社 | Multi-functional cyclic siloxane compound, siloxane-based polymer prepared from the compound and process for preparing dielectric film by using the polymer |
| CN101024632A (en) * | 2007-03-23 | 2007-08-29 | 东北林业大学 | Triazine series oligomer and its synthesizing method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110776635A (en) * | 2019-10-12 | 2020-02-11 | 华南理工大学 | Single-component intumescent flame retardant with free radical quenching function and preparation method and application thereof |
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