CN102731543B - 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 shown in the formula I. In the formula I, X is the element O or a group R, three Xs are element O, one X is the group R, the structural formula of the group R is shown in the formula II. In the formula II, the general formula of R1 is -HN(CH2CH2NH)n(CH2)3-, 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 synthetic method thereof, be specifically related to a kind of silicon-contained type N-substituted alkoxy hindered amine compound and synthetic method thereof.
Background technology
In recent years, in improved performance process, find that N-substituted alkoxy hindered amine has excellent flame retardant properties as the hindered amine of photostabilizer for a long time.N-substituted alkoxy hindered amine improves the one in kind as hindered amine, and have the feature of low reactivity, its chemical structure of general formula is:
Wherein, A is the auxiliary group connecting piperidyl, and B is substituted alkyl.
The free radical that the free radical scavenger interference of the efficient recyclable regenerative that the flame retardant efficiency of N-substituted alkoxy hindered amine in polyolefine is mainly produced by combustion decomposition and suppressing produces in combustion processes, and make it to be converted into that the compounds such as metastable alcohol, ketone realize.Research shows, N-substituted alkoxy hindered amine is applied to the thin goods of polyolefine such as fiber and film etc. and embodies excellent flame retarding efficiency, and low efficiently dense, adds about 0.5% and can reach satisfied flame retardant properties.Meanwhile, its good flame retardant synergism significantly can reduce the consumption of conventional flame retardant.Traditional N-substituted alkoxy hindered amine is generally the lower small molecules of molecular weight.Due to lower molecular weight, it easily causes the deficiency of the aspects such as easy migration, volatile and extracting in the polymeric material, reduces its effective concentration in the polymer thus causes low effort.Report in this type of fire-retardant FRW sees the patent US 5844026 of Ciba fine chemicals (Ciba Specialty Chemicals) the earliest.1998, the said firm was proposed N-substituted alkoxy hindered amines fire retardant Flamestab NOR 116 (see patent WO 2005005388, WO 2008003605) first, but it needs the conditions such as High Temperature High Pressure and synthesis technique is complicated.
N-substituted alkoxy hindered amine is applied to polymeric system as fire retarding synergist by prior art, more considers the contribution of N-substituted alkoxy hindered amine in fire-retardant and light is steady.And inventive concept of the present invention is: consider that silane coupling agent is the one type of silane simultaneously containing two kinds of different chemical character groups in molecule, by the interface of two kinds of opposed polarity materials is coupled together, silane coupling agent significantly can improve the consistency of inorganic combustion inhibitor and polymeric matrix, thus can improve the mechanical property of flame-retardant polymer system significantly; Meanwhile, by forming Si-O-C and Si-C crosslinking structure, silane coupling agent can also promote the formation of foamed char and the improvement of texture quality in polymer combustion process, also has certain synergistic effect to the flame retardant effect of conventional flame retardant.For this reason, the present invention is by being combined as a whole N-substituted alkoxy hindered amine and silane coupling agent, synthesize a kind of novel multifunctional flame-proof synergist, and compatibilization steady containing fire-retardant synergistic, light, can improve the performances such as its light is steady, mechanics further while raising flame-retardant polymer flame retardant properties simultaneously.
For achieving the above object, the technical solution used in the present invention is as follows:
The repeated structural unit of silicon-contained type N-substituted alkoxy hindered amine compound of the present invention is such as formula shown in I:
In formula I, X is element O or radicals R, and wherein, three X are element O, and an X is radicals R, and the structural formula of radicals R is such as formula shown in II:
In formula II, R
1general formula be-HN (CH
2cH
2nH)
n(CH
2)
3-, wherein, n is 0 ~ 2; R
2be general formula be-C
mh
2m+1alkyl, wherein, m is 1 ~ 8; R
3be general formula be-C
kh
2k-alkyl, wherein, k is 1 ~ 6; R
4, R
5be general formula be-C
ih
2i+1alkyl or general formula be-C
th
2t-1cycloalkyl, wherein, i is 1 ~ 8, t is 1 ~ 8.
The preparation method of silicon-contained type N-substituted alkoxy hindered amine compound of the present invention comprises the steps:
(1) by the first compound of having as shown in formula III and cyanuric chloride in the first organic solvent and under the effect of acid binding agent, carry out a substitution reaction of the triazine chlorine in ring atom of cyanuric chloride, the temperature of this substitution reaction is-10 ~ 10 DEG C; Wherein, the mol ratio of the first compound and cyanuric chloride is 1: 4 ~ 4: 1, and the mol ratio of described first compound and acid binding agent is 1: 5 ~ 5: 1;
In formula III, R
2be general formula be-C
mh
2m+1alkyl, wherein, m is 1 ~ 8; R
3be general formula be-C
kh
2k-alkyl, wherein, k is 1 ~ 6; R
4, R
5be general formula be-C
ih
2i+1alkyl or general formula be-C
th
2t-1cycloalkyl, wherein, i is 1 ~ 8, t is 1 ~ 8;
(2) when the pH of the reaction solution of a described substitution reaction is 6 ~ 7, its reaction system is warming up to 30 ~ 70 DEG C, and drip described acid binding agent and aminosilane, carry out two substitution reactions of the triazine chlorine in ring atom of the product that a substitution reaction obtains, generating structure formula is such as formula the intermediate product shown in IV and separated from its reaction system by this intermediate product, wherein, the aminosilane dripped in this step and the mol ratio of acid binding agent are 1: 4 ~ 4: 1.
In formula IV, R
2be general formula be-C
mh
2m+1alkyl, wherein, m is 1 ~ 8; R
3be general formula be-C
kh
2k-alkyl, wherein, k is 1 ~ 6; R
4, R
5be general formula be-C
ih
2i+1alkyl or general formula be-C
th
2t-1cycloalkyl, wherein, i is 1 ~ 8, t is 1 ~ 8; R
6general formula be-HN (CH
2cH
2nH)
n(CH
2)
3si (OCH
3)
3or-HN (CH
2cH
2nH)
q(CH
2)
3si (OH)
3, wherein, n is 0 ~ 2;
The general formula of described 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) by isolated intermediate product and described aminosilane in a second organic solvent and under the effect of described acid binding agent, carry out three substitution reactions of the triazine chlorine in ring atom of described intermediate product, in this three substitution reaction, temperature of reaction is 70 ~ 110 DEG C, and the mol ratio of aminosilane and acid binding agent is 1: 4 ~ 4: 1;
(4) when the pH of the reaction solution of three substitution reactions is 8 ~ 9, drip basic solution and carry out gel reaction, generate such as formula the final product shown in I; Wherein, described basic solution is ammoniacal liquor, bicarbonate aqueous solution or the metal hydroxides aqueous solution.
Further, the mol ratio of the first compound of the present invention and cyanuric chloride is 1: 1 ~ 1: 2, and the mol ratio of described first compound and acid binding agent is 1: 3 ~ 2: 1.
Further, the first organic solvent of the present invention is tetrahydrofuran (THF) or organic solvent of ketone.
Further, the present invention is acetone or butanone as the organic solvent of ketone of described first organic solvent.
Further, the second organic solvent of the present invention is dioxane or methyl-sulphoxide.
Further, acid binding agent of the present invention is bicarbonate aqueous solution, the metal hydroxides aqueous solution or organic amine.
Further, acid binding agent of the present invention is aqueous sodium hydroxide solution, sodium bicarbonate aqueous solution, triethylamine or N, N-di-isopropyl ethane.
Further, basic solution of the present 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: by the gel reaction being easy to the energy-conserving and environment-protective of chlorine substitution reaction and the silane coupling agent controlled of cyanuric chloride, N-substituted alkoxy hindered amine and silane coupling agent agent are combined as a whole, synthesize a kind of novel multifunctional flame-proof synergist, make its and compatibilization steady containing fire-retardant synergistic, light simultaneously, the performances such as its light is steady, mechanics can be improved further while raising flame-retardant polymer flame retardant properties.This synthetic method adopts silane gel reaction, containing a large amount of the structure of hindered amine in a molecule of the gel generated, crosslinking structure can be formed at polymeric surface layer after catching a large amount of macromole energetic free radical produced in polymer combustion degradation process, thus significantly improve structure and the quality of the layer of charcoal that polymer surfaces takes blocking effect, significantly promote the flame retarding efficiency of phosphorus system, expansion type flame-retardant polymer.In addition, silane gel reaction is simple to operate, and product is easily separated, and the deficiency of the aspects such as small molecules N-substituted alkoxy hindered amine easily moves in the polymeric material in order to overcome, volatile and extracting provides a kind of energy-conserving and environment-protective and effective method.
Summary of the invention
The object of the invention is to overcome the part or all of defect of prior art and a kind of new silicon-contained type N-substituted alkoxy hindered amine compound and synthetic method thereof are provided.
Embodiment
Below in conjunction with example, the present invention will be further described.
Embodiment 1:
7.376g (0.04mol) cyanuric chloride being dissolved in 80ml acetone is joined in the 500ml reactor that thermometer, magneton (magnetic stirring apparatus) are housed, low temperature thermostat bath temperature control also fully stirs, and makes reactant dispersed and keeps the temperature of reaction system to be-10 DEG C.By first compound (wherein, the R of 7.572g (0.01mol) structural formula as shown in formula III
2for alkyl-C
2h
5, R
3for alkyl-C
2h
4-, R
4for alkyl-CH
3, R
5for cycloalkyl-C
3h
5) and 8.70ml acid binding agent N, N-di-isopropyl ethane (0.05mol) is dissolved in 30ml acetone, dropwise drips in reactor with microsyringe, controls rate of addition, temperature of reaction controls at-10 DEG C, carries out a substitution reaction of the triazine chlorine in ring atom on cyanuric chloride.After dropping terminates, at-10 DEG C, low temperature continues reaction 5h, and now the pH of reaction solution is 6.0.After pour the solution in reactor into 250ml there-necked flask and move in heat-collecting magnetic stirring device, gradually the temperature of reaction system is brought up to 50 DEG C, drip in there-necked flask with microsyringe and 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 two substitution reactions carrying out the triazine chlorine in ring atom of the product that a substitution reaction obtains.After dropwising, at 50 DEG C, continue reaction 3h, generate intermediate product, the pH recording now reaction system is 7.0.Afterwards, steam on a rotary evaporator and desolventize acetone, be separated the intermediate product obtained in yellow thick liquid state, put it into after oven dry in vacuum drying oven is spent the night and take out, porphyrize is Powdered rear acetone/water (1: 1, volume ratio) wash 3 times, again put into vacuum drying oven vacuum-drying 24h after removing unreacted organic molecule, porphyrize is Powdered rear obtained intermediate product is faint yellow powdery.The productive rate of intermediate product is 97.56%.
The structural formula of intermediate product such as formula shown in IV, wherein, the R in formula IV
2for alkyl-C
2h
5, R
3for alkyl-C
2h
4-, R
4for alkyl-CH
3, R
5for cycloalkyl-C
3h
5, R
6for-HN (CH
2)
3si (OH)
3(R
6structural formula specifically such as formula shown in V).To the Infrared Characterization result of intermediate product be: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
0.005mol intermediate product is joined in 50ml dioxane solution (after the deoxygenation that dewaters distillation process), gradually temperature of reaction is brought up to 90 DEG C, drip in 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, heat up and keep back flow reaction 3h, the pH recording now reaction system is 8.0.Then, with microsyringe, 10ml saturated aqueous solution of sodium bicarbonate is dropwise instilled in there-necked flask, carry out gel reaction.After dropwising, continue to keep back flow reaction 1h, the pH recording now reaction system is 9.0.Terminate reaction, filter, washing, vacuum drying, the structural formula obtaining its repeating unit such as formula shown in I (wherein, X in formula I is for structural formula is such as formula the yellow powder final product silicon-contained type N-substituted alkoxy hindered amine compound of the radicals R shown in VI-1=a), and productive rate is 72.46%.As follows to the Infrared Characterization result of this final product:
FTIR(KBr，cm
-1)：1261.7(Si-C，wagging)，1026.2-1197.8(Si-O，stretching vibration)，802.8(Si-C)。
Final product silicon-contained type N-substituted alkoxy hindered amine compound (Si-NORs), oxidation inhibitor B215 and the Compatibilizer PP-g-MAH that synthesize in conventional expanded type fire retardant (IFR), the present embodiment is added in polypropylene (PP), wherein, IFR comprises ammonium polyphosphate (APP), tetramethylolmethane (PER) and trimeric cyanamide (MEL), and the mass ratio of three is APP: PER: MEL=2: 2: 1.According to the formula of table 1, the material of table 1 is joined in high speed mixer carry out Homogeneous phase mixing and extrude on the twin screw extruder, granulation, on vulcanizing press, be then hot pressed into the sample of needs, carry out the test of fire-retardant and uvioresistant performance.
Table 1
Flame retardant properties is tested: 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 all in UV-light accelerated deterioration case through UV-irradiation process.In ageing oven, ultraviolet lamp tube ultraviolet wavelength mainly concentrates on left and right, 313nm place, and power of lamp tube is 40W, 0.8W/m
2.The temperature inside the box maintains 60 DEG C.Expansion type flame-retarding PP sample takes out every for some time and surveys yellowness index and mechanical property.
Table 2 is the impact of Si-NORs (R=a) on the flame retardant effect of the fire-retardant PP of conventional expanded type.
Table 2 Si-NORs (R=a) is on the impact of the fire-retardant PP flame retardant effect of conventional expanded type
Table 3 is the impact of Si-NORs (R=a) on the fire-retardant PP uvioresistant performance (yellowness index) of conventional expanded type.
Table 3 Si-NORs (R=a) is on the impact of the fire-retardant PP yellowness index of conventional expanded type
Table 4 is the impact of Si-NORs (R=a) on fire-retardant PP uvioresistant performance impact (mechanical property) of conventional expanded type.
Table 4 Si-NORs (R=a) is on the impact of the fire-retardant PP mechanical property of conventional expanded type
Embodiment 2:
3.688g (0.02mol) cyanuric chloride being dissolved in 80ml butanone is joined in the 500ml reactor that thermometer, magneton (magnetic stirring apparatus) are housed, low temperature thermostat bath temperature control also fully stirs, and makes reactant dispersed and keeps the temperature of reaction system to be 10 DEG C.By first compound (wherein, the R of 7.572g (0.01mol) structural formula as shown in formula III
2for alkyl-C
2h
5, R
3for alkyl-C
2h
4-, R
4for alkyl-CH
3, R
5for cycloalkyl-C
3h
5) and the 15ml acid binding agent NaOH aqueous solution (2.0mol/L) be dissolved in 30ml butanone, dropwise drip in reactor with microsyringe simultaneously, control rate of addition, temperature of reaction controls at 10 DEG C, carries out a substitution reaction of the triazine chlorine in ring atom on cyanuric chloride.After dropping terminates, at 10 DEG C, low temperature continues reaction 2h, and now the pH of reaction solution is 6.5.After pour the solution in reactor into 250ml there-necked flask and move in heat-collecting magnetic stirring device, gradually the temperature of reaction system is brought up to 50 DEG C, in there-necked flask, drip the butanone solution 20ml and the 5ml acid binding agent NaOH aqueous solution (3.0mol/L) that are dissolved with 1.65ml3-aminopropyl ortho-siliformic acid (0.015mol) with microsyringe simultaneously, thus carry out two substitution reactions of the triazine chlorine in ring atom of the product that a substitution reaction obtains.After dropwising, at 50 DEG C, continue reaction 3h, generate intermediate product, the pH recording now reaction system is 7.5, and reaction terminates.Afterwards, steam on a rotary evaporator and desolventize butanone, be separated the intermediate product obtained in yellow thick liquid state, put it into after oven dry in vacuum drying oven is spent the night and take out, porphyrize is Powdered rear butanone/water (1: 1, volume ratio) wash 3 times, again put into vacuum drying oven vacuum-drying 24h after removing unreacted organic molecule, porphyrize is Powdered rear obtained intermediate product is faint yellow powdery.The productive rate of intermediate product is 83.25%.
The structural formula of intermediate product such as formula shown in IV, wherein, R
2for alkyl-C
2h
5, R
3for alkyl-C
2h
4-, R
4for alkyl-CH
3, R
5for cycloalkyl-C
3h
5, R
6for-HN (CH
2)
3si (OH)
3, specifically such as formula shown in V).To the Infrared Characterization result of intermediate product be: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
0.005mol intermediate product is joined in 50ml dioxane solution (after the deoxygenation that dewaters distillation process), gradually temperature of reaction is brought up to 90 DEG C, in there-necked flask, drip the butanone solution 10ml and the 5ml acid binding agent NaOH aqueous solution (2.0mol/L) that are dissolved with 1.10ml 3-aminopropyl ortho-siliformic acid (0.01mol) simultaneously with microsyringe simultaneously, carry out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heat up and keep back flow reaction 3h, the pH recording now reaction system is 8.0.Afterwards, with microsyringe 10ml saturated aqueous solution of sodium bicarbonate dropwise instilled in there-necked flask and carry out gel reaction.After dropwising, continue to keep back flow reaction 1h, the pH recording reaction system is 9.0.Terminate reaction, filter, washing, vacuum drying, the structural formula obtaining its repeating unit such as formula shown in I (wherein, X in formula I is for structural formula is such as formula the yellow powder final product silicon-contained type N-substituted alkoxy hindered amine compound of the radicals R shown in VI-1=a), and productive rate is 65.21%.As follows to the Infrared Characterization result of this final product:
FTIR(KBr，cm
-1)：1261.7(Si-C，wagging)，1026.2-1197.8(Si-O，stretching vibration)，802.8(Si-C)。
In PP, add the final product Si-NORs, oxidation inhibitor B215 and the Compatibilizer PP-g-MAH that synthesize in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and the mass ratio of three is APP: PER: MEL=2: 2: 1.According to the formula of table 1, the material of table 1 is joined in high speed mixer carry out Homogeneous phase mixing and extrude on the twin screw extruder, granulation, on vulcanizing press, be then hot pressed into the sample of needs, carry out the test of fire-retardant and uvioresistant performance.Its result as illustrated in tables 5-7.
Table 5 Si-NORs (R=a) is on the impact of the fire-retardant PP flame retardant effect of conventional expanded type
Table 6 Si-NORs (R=a) is on the impact of the fire-retardant PP yellowness index of conventional expanded type
Table 7 Si-NORs (R=a) is on the impact of the fire-retardant PP mechanical property of conventional expanded type
Embodiment 3:
1.844g (0.01mol) cyanuric chloride being dissolved in 80ml acetone is joined in the 500ml reactor that thermometer, magneton (magnetic stirring apparatus) are housed, low temperature thermostat bath temperature control also fully stirs, and makes reactant dispersed and keeps the temperature of reaction system to be 5 DEG C.By first compound (wherein, the R of 7.572g (0.01mol) structural formula as shown in formula III
2for alkyl-C
2h
5, R
3for alkyl-C
2h
4-, R
4for alkyl-CH
3, R
5for cycloalkyl-C
3h
5) and 0.870ml acid binding agent N, N-di-isopropyl ethane (0.005mol) is dissolved in 30ml acetone, dropwise drips in reactor with microsyringe, controls rate of addition, temperature of reaction controls at 5 DEG C, carries out a substitution reaction of the triazine chlorine in ring atom on cyanuric chloride.After dropping terminates, at 5 DEG C, low temperature continues reaction 3h, and now the pH of reaction solution is 6.5.After pour the solution in reactor into 250ml there-necked flask and move in heat-collecting magnetic stirring device, gradually the temperature of reaction system is brought up to 50 DEG C, drip in there-necked flask with microsyringe and 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 two substitution reactions carrying out the triazine chlorine in ring atom of the product that a substitution reaction obtains.After dropwising, at 50 DEG C, continue reaction 3h, generate intermediate product, the pH recording now reaction system is 7.5, and reaction terminates.Afterwards, steam on a rotary evaporator and desolventize acetone, be separated the intermediate product obtained in yellow thick liquid state, put it into after oven dry in vacuum drying oven is spent the night and take out, porphyrize is Powdered rear acetone/water (1: 1, volume ratio) wash 3 times, again put into vacuum drying oven vacuum-drying 24h after removing unreacted organic molecule, porphyrize is Powdered rear obtained intermediate product is faint yellow powdery.The productive rate of intermediate product is 98.26%.
The structural formula of intermediate product such as formula shown in IV, wherein, R
2for alkyl-C
2h
5, R
3for alkyl-C
2h
4-, R
4for alkyl-CH
3, R
5for cycloalkyl-C
3h
5, R
6for-HN (CH
2)
3si (OCH
3)
3.To the Infrared Characterization result of intermediate product be: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
0.005mol intermediate product is joined in 50ml dimethyl sulfoxide solution (after the deoxygenation that dewaters distillation process), gradually temperature of reaction is brought up to 90 DEG C, drip in 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, heat up and keep back flow reaction 3h, the pH recording now reaction system is 8.5.Then, with microsyringe the 10ml saturated ammonia aqueous solution dropwise instilled in there-necked flask and carry out gel reaction.After dropwising, continue to keep back flow reaction 1h, the pH recording reaction system is 9.0.Terminate reaction, filter, washing, vacuum drying, the structural formula obtaining its repeating unit such as formula shown in I (wherein, X in formula I is for structural formula is such as formula the yellow powder final product silicon-contained type N-substituted alkoxy hindered amine compound of the radicals R shown in VI-1=a), and productive rate is 75.98%.As follows to the Infrared Characterization result of this final product:
FTIR(KBr，cm
-1)：1261.7(Si-C，wagging)，1026.2-1197.8(Si-O，stretching vibration)，802.8(Si-C)。
In PP, add the final product Si-NORs, oxidation inhibitor B215 and the Compatibilizer PP-g-MAH that synthesize in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and the mass ratio of three is APP: PER: MEL=2: 2: 1.According to the formula of table 1, the material of table 1 is joined in high speed mixer carry out Homogeneous phase mixing and extrude on the twin screw extruder, granulation, on vulcanizing press, be then hot pressed into the sample of needs, carry out the test of fire-retardant and uvioresistant performance.Its result is as shown in table 8-10.
Table 8 Si-NORs (R=a) is on the impact of the fire-retardant PP flame retardant effect of conventional expanded type
Table 9 Si-NORs (R=a) is on the impact of the fire-retardant PP yellowness index of conventional expanded type
Table 10 Si-NORs (R=a) is on the impact of the fire-retardant PP mechanical property of conventional expanded type
Embodiment 4:
0.461g (0.0025mol) cyanuric chloride being dissolved in 80ml butanone is joined in the 500ml reactor that thermometer, magneton (magnetic stirring apparatus) are housed, low temperature thermostat bath temperature control also fully stirs, and makes reactant dispersed and keeps the temperature of reaction system to be 5 DEG C.By first compound (wherein, the R of 7.572g (0.0lmol) structural formula as shown in formula III
2for alkyl-C
2h
5, R
3for alkyl-C
2h
4-, R
4for alkyl-CH
3, R
5for cycloalkyl-C
3h
5) and the 0.67ml acid binding agent NaOH aqueous solution (3.0mol/L) be dissolved in 30ml butanone, dropwise drip in reactor with microsyringe simultaneously, control rate of addition, temperature of reaction controls at 5 DEG C, carries out a substitution reaction of the triazine chlorine in ring atom on cyanuric chloride.After dropping terminates, at 5 DEG C, low temperature continues reaction 3h, and now the pH of reaction solution is 7.0.After pour the solution in reactor into 250ml there-necked flask and move in heat-collecting magnetic stirring device, gradually the temperature of reaction system is brought up to 50 DEG C, in there-necked flask, drip the butanone solution 20ml and the 7.5ml acid binding agent NaOH aqueous solution (2.0mol/L) that are dissolved with 2.67ml 3-aminopropyl trimethoxysilane (0.015mol) with microsyringe simultaneously, thus carry out two substitution reactions of the triazine chlorine in ring atom of the product that a substitution reaction obtains.After dropwising, at 50 DEG C, continue reaction 3h, generate intermediate product, the pH recording now reaction system is 7.5, and reaction terminates.Afterwards, steam on a rotary evaporator and desolventize butanone, be separated the intermediate product obtained in yellow thick liquid state, put it into after oven dry in vacuum drying oven is spent the night and take out, porphyrize is Powdered rear butanone/water (1: 1, volume ratio) wash 3 times, again put into vacuum drying oven vacuum-drying 24h after removing unreacted organic molecule, porphyrize is Powdered rear obtained intermediate product is faint yellow powdery.The productive rate of intermediate product is 66.26%.
The structural formula of intermediate product such as formula shown in IV, wherein, R
2for alkyl-C
2h
5, R
3for alkyl-C
2h
4-, R
4for alkyl-CH
3, R
5for cycloalkyl-C
3h
5, R
6for-HN (CH
2)
3si (OCH
3)
3.To the Infrared Characterization result of intermediate product be: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-CF), 806.2 (Si-C).
0.005mol intermediate product is joined in 50ml dimethyl sulfoxide solution (after the deoxygenation that dewaters distillation process), gradually temperature of reaction is brought up to 90 DEG C, in there-necked flask, drip the butanone solution 10ml and the 5ml acid binding agent NaOH aqueous solution (2.0mol/L) that are dissolved with 1.78ml 3-aminopropyl trimethoxysilane (0.01mol) simultaneously with microsyringe simultaneously, carry out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heat up and keep back flow reaction 3h, the pH recording now reaction system is 8.5.Then, with microsyringe the 10ml saturated ammonia aqueous solution dropwise instilled in there-necked flask and carry out gel reaction.After dropwising, continue to keep back flow reaction 1h, the pH recording reaction system is 9.0.Terminate reaction, filter, washing, vacuum drying, the structural formula obtaining its repeating unit such as formula shown in I (wherein, X in formula I is for structural formula is such as formula the yellow powder final product silicon-contained type N-substituted alkoxy hindered amine compound of the radicals R shown in VI-1=a), and productive rate is 72.35%.As follows to the Infrared Characterization result of this final product:
FTIR(KBr，cm
-1)：1261.7(Si-C，wagging)，1026.2-1197.8(Si-O，stretching vibration)，802.8(Si-C)。
In PP, add the final product Si-NORs, oxidation inhibitor B215 and the Compatibilizer PP-g-MAH that synthesize in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and the mass ratio of three is APP: PER: MEL=2: 2: 1.According to the formula of table 1, the material of table 1 is joined in high speed mixer carry out Homogeneous phase mixing and extrude on the twin screw extruder, granulation, on vulcanizing press, be then hot pressed into the sample of needs, carry out the test of fire-retardant and uvioresistant performance.Its result is as shown in table 11-13.
Table 11 Si-NORs (R=a) is on the impact of the fire-retardant PP flame retardant effect of conventional expanded type
Table 12 Si-NORs (R=a) is on the impact of the fire-retardant PP yellowness index of conventional expanded type
Table 13 Si-NORs (R=a) is on the impact of the fire-retardant PP mechanical property of conventional expanded type
Embodiment 5:
3.688g (0.02mol) cyanuric chloride being dissolved in 80ml tetrahydrofuran (THF) is joined in the 500ml reactor that thermometer, magneton (magnetic stirring apparatus) are housed, low temperature thermostat bath temperature control also fully stirs, and makes reactant dispersed and keeps the temperature of reaction system to be 5 DEG C.By first compound (wherein, the R of 7.572g (0.01mol) structural formula as shown in formula III
2for alkyl-C
4h
9, R
3for alkyl-C
3h
6-, R
4for alkyl-C
6h
13, R
5for cycloalkyl-C
6h
11) and 4.18ml acid binding agent triethylamine (0.03mol) be dissolved in 30ml tetrahydrofuran (THF), dropwise drip in reactor with microsyringe, control rate of addition, temperature of reaction controls at 5 DEG C, carries out a substitution reaction of the triazine chlorine in ring atom on cyanuric chloride.After dropping terminates, at 5 DEG C, low temperature continues reaction 3h, and now the pH of reaction solution is 7.0.After pour the solution in reactor into 250ml there-necked flask and move in heat-collecting magnetic stirring device, gradually the temperature of reaction system is brought up to 30 DEG C, in there-necked flask, drip the tetrahydrofuran solution 20ml being dissolved with 3.21ml3-(2-aminoethylamino) propyl trimethoxy silicane (0.015mol) and acid binding agent 11.16ml triethylamine (0.06mol) with microsyringe, thus carry out two substitution reactions of the triazine chlorine in ring atom of the product that a substitution reaction obtains.After dropwising, at 30 DEG C, continue reaction 5h, generate intermediate product, the pH recording now reaction system is 8.0, and reaction terminates.Afterwards, steam on a rotary evaporator and desolventize tetrahydrofuran (THF), be separated the intermediate product obtained in yellow thick liquid state, put it into after oven dry in vacuum drying oven is spent the night and take out, porphyrize is Powdered rear tetrahydrofuran (THF)/water (1: 1, volume ratio) wash 3 times, again put into vacuum drying oven vacuum-drying 24h after removing unreacted organic molecule, porphyrize is Powdered rear obtained intermediate product is faint yellow powdery.The productive rate of intermediate product is 98.52%.
The structural formula of intermediate product such as formula shown in IV, wherein, R
2for alkyl-C
4h
9, R
3for alkyl-C
3h
6-, R
4for alkyl-C
6h
13, R
5for cycloalkyl-C
6h
11, R
6for-HN (CH
2cH
2nH) (CH
2)
3si (OCH
3)
3, specifically such as formula shown in VI-2.To the Infrared Characterization result of intermediate product be: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
0.005mol intermediate product is joined in 50ml dioxane solution (after the deoxygenation that dewaters distillation process), gradually temperature of reaction is brought up to 90 DEG C, in there-necked flask, drip the tetrahydrofuran solution 10ml being dissolved with 2.14ml 3-(2-aminoethylamino) propyl trimethoxy silicane (0.01mol) and 1.40ml acid binding agent triethylamine (0.01mol) simultaneously with microsyringe, carry out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heat up and keep back flow reaction 3h, the pH recording now reaction system is 8.5.Then, with microsyringe saturated for the 10ml NaOH aqueous solution dropwise instilled in there-necked flask and carry out gel reaction.After dropwising, continue to keep back flow reaction 1h, the pH recording reaction system is 9.0.Terminate reaction, filter, washing, vacuum drying, the structural formula obtaining its repeating unit such as formula shown in I (wherein, X in formula I is for structural formula is such as formula the radicals R=b shown in VII) yellow powder final product silicon-contained type N-substituted alkoxy hindered amine compound, productive rate is 76.12%.As follows to the Infrared Characterization result of this final product:
FTIR(KBr，cm
-1)：1261.7(Si-C，wagging)，1026.2-1197.8(Si-O，stretching vibration)，802.8(Si-C)。
In PP, add the final product Si-NORs, oxidation inhibitor B215 and the Compatibilizer PP-g-MAH that synthesize in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and the mass ratio of three is APP: PER: MEL=2: 2: 1.According to the formula of table 1, the material of table 1 is joined in high speed mixer carry out Homogeneous phase mixing and extrude on the twin screw extruder, granulation, on vulcanizing press, be then hot pressed into the sample of needs, carry out the test of fire-retardant and uvioresistant performance.Its result is as shown in table 14-16.
Table 14 Si-NORs (R=b) is on the impact of the fire-retardant PP flame retardant effect of conventional expanded type
Table 15 Si-NORs (R=b) is on the impact of the fire-retardant PP yellowness index of conventional expanded type
Table 16 Si-NORs (R=b) is on the impact of the fire-retardant PP mechanical property of conventional expanded type
Embodiment 6:
3.688g (0.02mol) cyanuric chloride being dissolved in 80ml tetrahydrofuran (THF) is joined in the 500ml reactor that thermometer, magneton (magnetic stirring apparatus) are housed, low temperature thermostat bath temperature control also fully stirs, and makes reactant dispersed and keeps the temperature of reaction system to be 5 DEG C.By first compound (wherein, the R of 7.572g (0.01mol) structural formula as shown in formula III
2for alkyl-C
4h
9, R
3for alkyl-C
3h
6-, R
4for alkyl-C
6h
13, R
5for cycloalkyl-C
6h
11) and 10ml acid binding agent NaHCO
3the aqueous solution (3.0mol/L) is dissolved in 30ml tetrahydrofuran (THF), dropwise drips with microsyringe in reactor simultaneously, and control rate of addition, temperature of reaction controls at 5 DEG C, carries out a substitution reaction of the triazine chlorine in ring atom on cyanuric chloride.After dropping terminates, at 5 DEG C, low temperature continues reaction 3h, and now the pH of reaction solution is 7.0.After pour the solution in reactor into 250ml there-necked flask and move in heat-collecting magnetic stirring device, gradually the temperature of reaction system is brought up to 70 DEG C, in there-necked flask, drip the tetrahydrofuran solution 20ml and the 1.25ml acid binding agent NaHCO that are dissolved with 3.21ml 3-(2-aminoethylamino) propyl trimethoxy silicane (0.015mol) with microsyringe simultaneously
3the aqueous solution (3.0mol/L), thus two substitution reactions carrying out the triazine chlorine in ring atom of the product that a substitution reaction obtains.After dropwising, at 70 DEG C, continue reaction 1h, generate intermediate product, the pH recording now reaction system is 8.0, and reaction terminates.Afterwards, steam on a rotary evaporator and desolventize tetrahydrofuran (THF), be separated the intermediate product obtained in yellow thick liquid state, put it into after oven dry in vacuum drying oven is spent the night and take out, porphyrize is Powdered rear tetrahydrofuran (THF)/water (1: 1, volume ratio) wash 3 times, again put into vacuum drying oven vacuum-drying 24h after removing unreacted organic molecule, porphyrize is Powdered rear obtained intermediate product is faint yellow powdery.The productive rate of intermediate product is 95.43%.
The structural formula of intermediate product such as formula shown in IV, wherein, R
2for alkyl-C
4h
9, R
3for alkyl-C
3h
6-, R
4for alkyl-C
6h
13, R
5for cycloalkyl-C
6h
11, R
6for-HN (CH
2cH
2nH) (CH
2)
3si (OCH
3)
3, specifically such as formula shown in VI-2.To the Infrared Characterization result of intermediate product be: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
0.005mol intermediate product is joined in 50ml dimethyl sulfoxide solution (after the deoxygenation that dewaters distillation process), gradually temperature of reaction is brought up to 90 DEG C, in there-necked flask, drip the tetrahydrofuran solution 10ml and the 10ml acid binding agent NaHCO that are dissolved with 2.14ml 3-(2-aminoethylamino) propyl trimethoxy silicane (0.01mol) simultaneously with microsyringe simultaneously
3the aqueous solution (1.0mol/L), carries out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heat up and keep back flow reaction 3h, the pH recording now reaction system is 9.0.Then, with microsyringe saturated for the 10ml NaOH aqueous solution dropwise instilled in there-necked flask and carry out gel reaction.After dropwising, continue to keep back flow reaction 1h, the pH recording reaction system is 9.5.Terminate reaction, filter, washing, vacuum drying, the structural formula obtaining its repeating unit such as formula shown in I (wherein, X in formula I is for structural formula is such as formula the radicals R=b shown in VII) yellow powder final product silicon-contained type N-substituted alkoxy hindered amine compound, productive rate is 75.24%.As follows to the Infrared Characterization result of this final product:
FTIR(KBr，cm
-1)：1261.7(Si-C，wagging)，1026.2-1197.8(Si-O，stretching vibration)，802.8(Si-C)。
In PP, add the final product Si-NORs, oxidation inhibitor B215 and the Compatibilizer PP-g-MAH that synthesize in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and the mass ratio of three is APP: PER: MEL=2: 2: 1.According to the formula of table 1, the material of table 1 is joined in high speed mixer carry out Homogeneous phase mixing and extrude on the twin screw extruder, granulation, on vulcanizing press, be then hot pressed into the sample of needs, carry out the test of fire-retardant and uvioresistant performance.Its result is as shown in table 17-19.
Table 17 Si-NORs (R=b) is on the impact of the fire-retardant PP flame retardant effect of conventional expanded type
Table 18 Si-NORs (R=b) is on the impact of the fire-retardant PP yellowness index of conventional expanded type
Table 19 Si-NORs (R=b) is on the impact of the fire-retardant PP mechanical property of conventional expanded type
Embodiment 7:
3.688g (0.02mol) cyanuric chloride being dissolved in 80ml acetone is joined in the 500ml reactor that thermometer, magneton (magnetic stirring apparatus) are housed, low temperature thermostat bath temperature control also fully stirs, and makes reactant dispersed and keeps the temperature of reaction system to be 5 DEG C.By first compound (wherein, the R of 7.572g (0.01mol) structural formula as shown in formula III
2for alkyl-C
8h
17, R
3for alkyl-C
6h
12-, R
4for cycloalkyl-C
8h
15, R
5for alkyl-C
8h
17) and 4.18ml acid binding agent triethylamine (0.03mol) be dissolved in 30ml acetone, dropwise drip in reactor with microsyringe, control rate of addition, temperature of reaction controls at 5 DEG C, carries out a substitution reaction of the triazine chlorine in ring atom on cyanuric chloride.After dropping terminates, at 5 DEG C, low temperature continues reaction 3h, and now the pH of reaction solution is 6.5.After pour the solution in reactor into 250ml there-necked flask and move in heat-collecting magnetic stirring device, gradually temperature of reaction system is brought up to 50 DEG C, in there-necked flask, drip the acetone soln 20ml being dissolved with 3.86ml diethylenetriamine base propyl trimethoxy silicane (0.015mol) and 2.79ml acid binding agent triethylamine (0.015mol) with microsyringe, thus carry out two substitution reactions of the triazine chlorine in ring atom of the product that a substitution reaction obtains.After dropwising, at 50 DEG C, continue reaction 3h, generate intermediate product, the pH recording now reaction system is 7.5, and reaction terminates.Afterwards, steam on a rotary evaporator and desolventize acetone, be separated the intermediate product obtained in yellow thick liquid state, put it into after oven dry in vacuum drying oven is spent the night and take out, porphyrize is Powdered rear acetone/water (1: 1, volume ratio) wash 3 times, again put into vacuum drying oven vacuum-drying 24h after removing unreacted organic molecule, porphyrize is Powdered rear obtained intermediate product is faint yellow powdery.The productive rate of intermediate product is 99.13%.
The structural formula of intermediate product such as formula shown in IV, wherein, R
2for alkyl-C
8h
17, R
3for alkyl-C
6h
12-, R
4for cycloalkyl-C
8h
15, R
5for alkyl-C
8h
17, R
6for-HN (CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, specifically such as formula shown in VIII.To the Infrared Characterization result of intermediate product be: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
0.005mol intermediate product is joined in 50ml dioxane solution (after the deoxygenation that dewaters distillation process), gradually temperature of reaction is brought up to 70 DEG C, in there-necked flask, drip the acetone soln 20ml being dissolved with 2.57ml diethylenetriamine base propyl trimethoxy silicane (0.01mol) and 8.36ml acid binding agent triethylamine (0.04mol) simultaneously with microsyringe, carry out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heat up and keep back flow reaction 5h, the pH recording now reaction system is 8.5.Then, with microsyringe the 5ml saturated ammonia aqueous solution dropwise instilled in there-necked flask and carry out gel reaction.After dropwising, continue to keep back flow reaction 2h, the pH recording reaction system is 9.0.Terminate reaction, filter, washing, vacuum drying, obtain the yellow powder final product silicon-contained type N-substituted alkoxy hindered amine compound of structural formula such as formula (wherein, the X in formula I is for structural formula is such as formula the radicals R=c shown in IX) shown in I of its repeating unit, productive rate is 82.10%.As follows to the Infrared Characterization result of this final product:
FTIR(KBr，cm
-1)：1261.7(Si-C，wagging)，1026.2-1197.8(Si-O，stretching vibration)，802.8(Si-C)。
In PP, add the final product Si-NORs, oxidation inhibitor B215 and the Compatibilizer PP-g-MAH that synthesize in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and the mass ratio of three is APP: PER: MEL=2: 2: 1.According to the formula of table 1, the material of table 1 is joined in high speed mixer carry out Homogeneous phase mixing and extrude on the twin screw extruder, granulation, on vulcanizing press, be then hot pressed into the sample of needs, carry out the test of fire-retardant and uvioresistant performance.Its result is as shown in table 20-22.
Table 20 Si-NORs (R=c) is on the impact of the fire-retardant PP flame retardant effect of conventional expanded type
Table 21 Si-NORs (R=b) is on the impact of the fire-retardant PP yellowness index of conventional expanded type
Table 22 Si-NORs (R=c) is on the impact of the fire-retardant PP mechanical property of conventional expanded type
Embodiment 8:
3.688g (0.02mol) cyanuric chloride being dissolved in 80ml tetrahydrofuran (THF) is joined in the 500ml reactor that thermometer, magneton (magnetic stirring apparatus) are housed, low temperature thermostat bath temperature control also fully stirs, and makes reactant dispersed and keeps the temperature of reaction system to be 5 DEG C.By first compound (wherein, the R of 7.572g (0.01mol) structural formula as shown in formula III
2for alkyl-C
8h
17, R
3for alkyl-C
6h
12-, R
4for cycloalkyl-C
8h
15, R
5for alkyl-C
8h
17) and 10ml acid binding agent NaHCO
3the aqueous solution (3.0mol/L) is dissolved in 30ml tetrahydrofuran (THF), dropwise drips with microsyringe in reactor simultaneously, and control rate of addition, temperature of reaction controls at 5 DEG C, carries out a substitution reaction of the triazine chlorine in ring atom on cyanuric chloride.After dropping terminates, at 5 DEG C, low temperature continues reaction 3h, and now the pH of reaction solution is 6.5.After pour the solution in reactor into 250ml there-necked flask and move in heat-collecting magnetic stirring device, gradually the temperature of reaction system is brought up to 50 DEG C, in there-necked flask, drip the tetrahydrofuran solution 20ml and the 5ml acid binding agent NaHCO that are dissolved with 3.86ml diethylenetriamine base propyl trimethoxy silicane (0.015mol) with microsyringe simultaneously
3the aqueous solution (3.0mol/L), thus two substitution reactions carrying out the triazine chlorine in ring atom of the product that a substitution reaction obtains.After dropwising, at 50 DEG C, continue reaction 3h, generate intermediate product, the pH recording now reaction system is 7.5, and reaction terminates.Afterwards, steam on a rotary evaporator and desolventize tetrahydrofuran (THF), be separated the intermediate product obtained in yellow thick liquid state, put it into after oven dry in vacuum drying oven is spent the night and take out, porphyrize is Powdered rear tetrahydrofuran (THF)/water (1: 1, volume ratio) wash 3 times, again put into vacuum drying oven vacuum-drying 24h after removing unreacted organic molecule, porphyrize is Powdered rear obtained intermediate product is faint yellow powdery.The productive rate of intermediate product is 99.25%.
The structural formula of intermediate product such as formula shown in IV, wherein, R
2for alkyl-C
8h
17, R
3for alkyl-C
6h
12-, R
4for cycloalkyl-C
8h
15, R
5for alkyl-C
8h
17, R
6for-HN (CH
2cH
2nH)
2(CH
2)
3si (OCH
3)
3, specifically such as formula shown in VIII.To the Infrared Characterization result of intermediate product be: FTIR (KBr, cm
-1): 1050.7-1117.9 (Si-O, stretching vibration), 844.3 (tr-Cl), 806.2 (Si-C).
0.005mol intermediate product is joined in 50ml dimethyl sulfoxide solution (after the deoxygenation that dewaters distillation process), gradually temperature of reaction is brought up to 110 DEG C, in there-necked flask, drip the tetrahydrofuran solution 10ml and the 2.5ml acid binding agent NaHCO that are dissolved with 2.57ml diethylenetriamine base propyl trimethoxy silicane (0.01mol) simultaneously with microsyringe simultaneously
3the aqueous solution (1.0mol/L), carries out three substitution reactions of the triazine chlorine in ring atom of intermediate product.After dropwising, heat up and keep back flow reaction 1h, the pH recording now reaction system is 8.5.Then, with microsyringe saturated for the 20ml NaOH aqueous solution dropwise instilled in there-necked flask and carry out gel reaction.After dropwising, continue to keep back flow reaction 0.5h, the pH recording reaction system is 9.5.Terminate reaction, filter, washing, vacuum drying, obtain the yellow powder final product silicon-contained type N-substituted alkoxy hindered amine compound of structural formula such as formula (wherein, the X in formula I is for structural formula is such as formula the radicals R=c shown in IX) shown in I of its repeating unit, productive rate is 80.23%.As follows to the Infrared Characterization result of this final product:
FTIR(KBr，cm
-1)：1261.7(Si-C，wagging)，1026.2-1197.8(Si-O，stretching vibration)，802.8(Si-C)。
In PP, add the final product Si-NORs, oxidation inhibitor B215 and the Compatibilizer PP-g-MAH that synthesize in IFR, the present embodiment, wherein, IFR comprises APP, PER and MEL, and the mass ratio of three is APP: PER: MEL=2: 2: 1.According to the formula of table 1, the material of table 1 is joined in high speed mixer carry out Homogeneous phase mixing and extrude on the twin screw extruder, granulation, on vulcanizing press, be then hot pressed into the sample of needs, carry out the test of fire-retardant and uvioresistant performance.Its result is as shown in table 23-25.
Table 23 Si-NORs (R=c) is on the impact of the fire-retardant PP flame retardant effect of conventional expanded type
Table 24 Si-NORs (R=b) is on the impact of the fire-retardant PP yellowness index of conventional expanded type
Table 25 Si-NORs (R=c) is on the impact of the fire-retardant PP mechanical property of conventional expanded type
Can be seen by above the performance test results, the N-substituted alkoxy hindered amine compound Si-NORs of different structure of the present invention has excellent flame retardant synergism, 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 be had molten drop phenomenon from during burning, cannot be brought up to V-0 grade by flame retardant properties the best by minimum V-2 grade, makes the fire-retardant PP of conventional expanded type reach the flame-retardant test criteria of extensively accreditation.This effect carrys out the unique texture as Si-NORs of the present invention.In the combustion processes of PP, on the one hand, Si-NORs can catch the energetic free radical of PP burning generation at the free radical scavenger that gas-phase decomposition produces, the free radical reaction in interference combustion processes; On the other hand, Si-NORs can also increase the melt strength in PP combustion processes in Si-O-C and the Si-C crosslinking structure of condensed phase decomposition generation, promote the foaming form of foamed char, promotes the thermostability of foamed char and obstruct effect further.In addition, shown by the yellowness index of expansion type flame-retarding PP and mechanical experimental results, compared to the expansion type flame-retarding PP not adding N-substituted alkoxy hindered amine compound, after adding the N-substituted alkoxy hindered amine compound of 1wt%, the yellowing of expansion type flame-retarding PP under ultraviolet radiation condition and mechanical property deterioration degree obtain improvement in various degree, and along with the increase of ultraviolet radiation time, its yellowing and mechanical property deterioration degree weaken more obvious.Therefore, the N-substituted alkoxy hindered amine compound of the present invention's synthesis contains the steady and compatibilization of fire-retardant synergistic, light, can improve the performances such as its light is steady, mechanics further while the traditional flame-retardant polymer flame retardant properties of raising, be a kind of novel multifunctional flame-proof synergist.
Claims (9)
1. a silicon-contained type N-substituted alkoxy hindered amine compound, is characterized in that, the structure of its repeating unit is such as formula shown in I:
In formula I, X is element O or radicals R, and wherein, three X are element O, and an X is radicals R, and the structural formula of radicals R is such as formula shown in II:
In formula II, R
1general formula be-HN (CH
2cH
2nH)
n(CH
2)
3-, wherein, n is 0 ~ 2; R
2be general formula be-C
mh
2m+1alkyl, wherein, m is 1 ~ 8; R
3be general formula be-C
kh
2k-alkyl, wherein, k is 1 ~ 6; R
4, R
5be general formula be-C
ih
2i+1alkyl or general formula be-C
th
2t-1cycloalkyl, wherein, i is 1 ~ 8, t is 1 ~ 8.
2. a preparation method for the compound of claim 1, is characterized in that, comprises the steps:
(1) by the first compound of having as shown in formula III and cyanuric chloride in the first organic solvent and under the effect of acid binding agent, carry out a substitution reaction of the triazine chlorine in ring atom of cyanuric chloride, the temperature of this substitution reaction is-10 ~ 10 DEG C; Wherein, the mol ratio of the first compound and cyanuric chloride is 1: 4 ~ 4: 1, and the mol ratio of described first compound and acid binding agent is 1: 5 ~ 5: 1;
In formula III, R
2be general formula be-C
mh
2m+1alkyl, wherein, m is 1 ~ 8; R
3be general formula be-C
kh
2k-alkyl, wherein, k is 1 ~ 6; R
4, R
5be general formula be-C
ih
2i+1alkyl or general formula be-C
th
2t-1cycloalkyl, wherein, i is 1 ~ 8, t is 1 ~ 8;
(2) when the pH of the reaction solution of a described substitution reaction is 6 ~ 7, its reaction system is warming up to 30 ~ 70 DEG C, and drip described 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 product that a substitution reaction obtains, when the pH that two substitution reactions proceed to reaction solution is 7 ~ 8, generate such as formula the intermediate product shown in IV, then described intermediate product is separated from its reaction system;
In formula IV, R
2be general formula be-C
mh
2m+1alkyl, wherein, m is 1 ~ 8; R
3be general formula be-C
kh
2k-alkyl, wherein, k is 1 ~ 6; R
4, R
5be general formula be-C
ih
2i+1alkyl or general formula be-C
th
2t-1cycloalkyl, wherein, i is 1 ~ 8, t is 1 ~ 8; R
6general formula be-HN (CH
2cH
2nH)
n(CH
2)
3si (OCH
3)
3or-HN (CH
2cH
2nH)
q(CH
2)
3si (OH)
3, wherein, n is 0 ~ 2;
The general formula of described 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) by isolated intermediate product and described aminosilane in a second organic solvent and under the effect of described acid binding agent, carry out three substitution reactions of the triazine chlorine in ring atom of described intermediate product, in this three substitution reaction, temperature of reaction is 70 ~ 110 DEG C, and the mol ratio of aminosilane and acid binding agent is 1: 4 ~ 4: 1;
(4) when the pH of the reaction solution of three substitution reactions is 8 ~ 9, drip basic solution and carry out gel reaction, generate such as formula the final product shown in I; Wherein, described basic solution 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 described first compound and cyanuric chloride is 1: 1 ~ 1: 2, and the mol ratio of described first compound and acid binding agent is 1: 3 ~ 2: 1.
4. preparation method according to claim 2, is characterized in that: described first organic solvent is tetrahydrofuran (THF) or organic solvent of ketone.
5. preparation method according to claim 4, is characterized in that: the organic solvent of ketone as described first organic solvent is acetone or butanone.
6. preparation method according to claim 2, is characterized in that: described second organic solvent is dioxane or methyl-sulphoxide.
7. preparation method according to claim 2, is characterized in that: described 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: described 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: described basic solution is saturated ammoniacal liquor, sodium hydroxide solution or saturated aqueous solution of sodium bicarbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210225852.1A CN102731543B (en) | 2012-06-29 | 2012-06-29 | Siliceous N-substituted alkyloxy hindered amine compound and its preparation method |
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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 |
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