CN101445520B - Phosphoric organic silicon compound, preparation method and application thereof - Google Patents
Phosphoric organic silicon compound, preparation method and application thereof Download PDFInfo
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- CN101445520B CN101445520B CN2007101780867A CN200710178086A CN101445520B CN 101445520 B CN101445520 B CN 101445520B CN 2007101780867 A CN2007101780867 A CN 2007101780867A CN 200710178086 A CN200710178086 A CN 200710178086A CN 101445520 B CN101445520 B CN 101445520B
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- 0 C*c1c(-c(c(*)c(*)c(*)c2*)c2P(O2)=O)c2c(*)c(*)c1* Chemical compound C*c1c(-c(c(*)c(*)c(*)c2*)c2P(O2)=O)c2c(*)c(*)c1* 0.000 description 1
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Abstract
The invention discloses a phosphoric organic silicon compound, a preparation method and application thereof. The structural formula of the phosphoric organic silicon compound is shown as Figure 1, wherein, R1, R2, R3 and R4 are selected from C1-C5 alkyl, C1-C5 alkoxy, aryl, aryl substituted by halogen and aroxy; R5 and R6 are C0-C5 alkylidene groups; R7-R14 are selected from hydrogen atom, C1-C5 alkyl, nitro, the C1-C5 alkoxy, aryl, the aryl substituted by the halogen and the aroxy; and n is 1-10. The preparation method comprises performing an addition reaction of an active phosphorus-hydrogen bond in a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivative and siloxane containing two carbon-carbon double bonds to produce the novel phosphoric organic silicon compound. The compound contains two elements namely phosphorus and silicon which have flame retardant property, and can be taken as an additive flame retardant for inflaming retarding of high molecular materials.
Description
Technical field
The present invention relates to a kind of organic silicon compound containing phosphorus and preparation method thereof and application.
Background technology
Macromolecular materials such as Resins, epoxy, polyester and engineering plastics are widely used in many aspects of the development of the national economy; But,, therefore need to add brominated antimony organic compound or the resin of containing usually to obtain satisfied flame retardant properties because macromolecular material itself do not possess fire retardant performance.Yet the brominated antimony fire retardant that contains can discharge a large amount of poisonous and hazardous materials in meeting the fire burns process, cause environmental pollution, be detrimental to health.In recent years, the phosphorous and siliceous fire retardant of environmental type becomes people's research and the focus of paying close attention to.Phosphonium flame retardant is considered to the brominated effective surrogate that contains the antimony fire retardant, and wherein with 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound (DOPO) becomes a very active research field for the phosphonium flame retardant of reactive intermediate.The adduct that patent CN1423678 (Dow) discloses DOPO and para benzoquinone is applied to the method for fire retarding epoxide resin veneer sheet, can make Resins, epoxy have the flame retardant properties that satisfies UL94 V-0 standard when keeping excellent machinability.Patent CN1563152 discloses and has a kind ofly prepared the method for phosphorous polymer by aryl phosphonyl dichloride, DOPO and fragrant quinone adduct by polyreaction, and prepared phosphorous polymer can make Resins, epoxy, polymeric amide and vibrin reach UL94 V-0 level flame retardant rating.Patent US2001000377 discloses a kind of preparation method of fire retarding epoxide resin, and this method obtains phosphorous epoxy resin with DOPO and dihydroxyphenyl propane or o-cresol formaldehyde epoxy resin reaction, solidifies with DDS to obtain the Resins, epoxy that flame retardant rating reaches UL94 V-0 again.Patent US20020035233 discloses a kind of preparation method of fire retarding epoxide resin, this method is carried out chain extending reaction with the adduct of DOPO and benzoquinones or naphthoquinones reaction with Resins, epoxy and is obtained Resins, epoxy, is cured with linear phenolic resin and obtains the good epoxy resin cured product of flame retardant properties.Patent JP2003055436 also discloses a kind of preparation method of fire retarding epoxide resin, and this method obtains phosphorous epoxy resin with DOPO and Resins, epoxy reaction, solidifies the Resins, epoxy that obtains flame retardant rating UL94 V-0 with Dyhard RU 100 again.Patent US6441067B1 discloses a kind of preparation method of phosphorous amine curing agent, and the phosphorous amine curing agent that obtains is used for cured epoxy resin, can obtain the good cured article of flame retardant properties.(Appl Organomet Chem1999 such as Edward G.Shockey and Frank J.Feher; 13 (4): 311-27 and Chem Commun 1998; (3): 323-4) reported the application of a kind of silicon-containing compound and fire-retardant aspect thereof.In a word, above-mentioned research all is the fire retardant based on phosphorous or silicon-containing compound.
It is reported to have the effect of cooperative flame retardant when phosphoric and element silicon coexistence.Patent CN1922252 discloses a kind of preparation method of epoxy laminate, polysiloxane and phosphate compounds are used for epoxy laminate jointly, make to have good flame retardant property and mechanical property after Resins, epoxy-glass-base laminated material curing.Patent US20050245670, JP2000327897 (Sumitomo Dow) discloses a kind of preparation method of polycarbonate, polysiloxane and phosphine nitrile or phosphate compounds jointly as the fire retardant of polycarbonate, have been obtained good flame retardancy (UL94 V-0) and mechanical property (shock strength＞60kgcm/cm).Studies show that phosphoric and element silicon use simultaneously and have the cooperative flame retardant effect really, have tangible advantage than independent use phosphonium flame retardant or brominated flame-retardant, help improving the over-all properties of fire retardant material simultaneously.Therefore, study the BACN that contains phosphoric and element silicon simultaneously and have important scientific meaning and potential using value.
Summary of the invention
The purpose of this invention is to provide a kind of organic silicon compound containing phosphorus and preparation method thereof.
Organic silicon compound containing phosphorus provided by the present invention, its structure be suc as formula shown in the I,
Wherein, R
1, R
2, R
3, R
4Be selected from aryl, aryloxy that alkoxyl group, aryl, the halogen of alkyl, the C1-C5 of C1-C5 replace; R
5With R
6Alkylidene group for C0-C5; R
7-R
14Be selected from aryl, aryloxy that alkyl, nitro, the alkoxyl group of C1-C5, aryl, the halogen of hydrogen atom, C1-C5 replace; N is 1-10.
Here, need to prove " R
5With R
6Alkylidene group for C0-C5 ", expression: work as R
5With R
6During for the alkylidene group of C0, in fact R5 and R6 do not exist, and the Siliciumatom in the formula I structure is connected with the ethylidene of phosphorus atom by two carbon.
Preferably, R
1, R
2, R
3, R
4Be selected from methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trifluoromethyl, trifluoromethyl, two (trifluoromethyl) phenyl, benzyl, benzyl ethyl and phenoxy group.R
5With R
6Be selected from methylene radical, ethylidene, propylidene and butylidene.R
7-R
14Be selected from hydrogen atom, methyl, ethyl, propyl group, nitro, methoxyl group, oxyethyl group, propoxy-, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trifluoromethyl, trifluoromethyl, two (trifluoromethyl) phenyl, benzyl, benzyl ethyl and phenoxy group.N is 1-4.
The preparation method of organic silicon compound containing phosphorus of the present invention, be under catalyzer or action of free radical initiator, by 9 of formula II structure, the 10-dihydro-9-oxy is assorted-and the siloxanes of 10-phospho hetero phenanthrene-10-oxide derivative and formula III structure reacts, and obtains the organic silicon compound containing phosphorus of described formula I structure;
Formula II is identical with formula I with each substituent definition in the formula III, here, and need be to " R in the formula III
5With R
6Alkylidene group for C0-C5 " describe: work as R
5With R
6During for the alkylidene group of C0, in fact represent that R5 and R6 do not exist, Siliciumatom in the formula III structure directly is connected with the end carbon-carbon double bond, when preparing organic silicon compound containing phosphorus of the present invention with this starting compound, Siliciumatom is connected with the ethylidene of phosphorus atom by two carbon in the gained organic silicon compound containing phosphorus.
In the reaction, 9 of formula II structure, the 10-dihydro-9-oxy is assorted-and the weight ratio of the siloxanes of 10-phospho hetero phenanthrene-10-oxide derivative and formula III structure is 100: 1-400.
In the preparation process of the present invention, catalyzer is selected from Platinic chloride, palladium chloride, Trichlororhodium, perhaps, and the title complex of Platinic chloride, palladium chloride, Trichlororhodium.Wherein, the title complex of Platinic chloride, palladium chloride, Trichlororhodium is X (PPh
3)
3Cl, X (PPh
3)
3Cl
2, X (PPh
3)
3Cl
3, X (POEt
3)
3Cl, X (POEt
3)
3H
2(CO), X represents platinum, palladium and rhodium.Radical initiator comprises one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), hydrogen peroxide, isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, the special butyl ester of peroxidation phenylformic acid, peroxide tert pivalate ester, peroxy dicarbonate diisobutyl ester, di-cyclohexylperoxy dicarbonate, Potassium Persulphate, the ammonium persulphate.
The solvent of reaction comprises methyl alcohol, ethanol, propyl alcohol, Virahol, benzene,toluene,xylene, trimethylbenzene, chlorobenzene, oil of mirbane, hexone, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, methyl tertbutyl ketone, methyl acetate, ethyl acetate, butylacetate, acetate glycidyl ester, tetrahydrofuran (THF), dioxane, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide and the mixture that mixes by arbitrary proportion thereof.Temperature of reaction is 30-180 ℃; Reaction times is 1-72 hour.
Another object of the present invention provides the purposes of organic silicon compound containing phosphorus of the present invention.
Contain phosphoric and element silicon in the chemical structure of organic silicon compound containing phosphorus of the present invention simultaneously, the cooperative flame retardant effect of phosphorus and element silicon makes it have good flame retardant property, can be used as the fire retardant of macromolecular materials such as Resins, epoxy, resol, polyolefine, polyester, polymeric amide, polyethers, polysulfones and engineering plastics and be used widely, the inventor has also confirmed this point by test, and, add the mechanical property that organic silicon compound containing phosphorus of the present invention can also promote material.Therefore, organic silicon compound containing phosphorus of the present invention also belongs to protection scope of the present invention as the purposes of fire retardant.
The present invention utilizes 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO) derivative in active phosphorus hydrogen bond generate a kind of novel phosphorus-containing silicoorganic compound with containing the siloxanes generation addition reaction of two carbon-carbon double bonds; This compound contains phosphorus and two kinds of elements with flame retardant properties of silicon simultaneously, can be used as additive flame retardant and is used for the fire-retardant of macromolecular material.
Description of drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum spectrogram of compound one;
Fig. 2 is the MALDI-TOF mass spectrum of compound one.
Embodiment
The synthetic of organic silicon compound containing phosphorus of the present invention can adopt following process to carry out:
With 9 of 100 weight parts, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide derivative (formula II) and the siloxanes that contains two carbon-carbon double bonds (formula III) of 1-400 weight part and the organic solvent of 0-1000 weight part add in the there-necked flask, and adding 0.05-1mL concentration is 1.0 * 10
-6The coordination reaction transition-metal catalyst of-1.0mol/L or the free radical reaction initiator of 1-100 weight part, heated and stirred reaction under nitrogen protection.Temperature of reaction is 30-180 ℃, reaction times 1-72 hour; Decompression removes the lower-boiling impurity that generates in the dereaction, cools to 60 ℃, removes the impurity that generates in the dereaction 3-5 time with solvent wash; Underpressure distillation removes the postcooling that desolvates, and obtains described organic silicon compound containing phosphorus.
Wherein, 9, the 10-dihydro-9-oxy is assorted-and the structure of 10-phospho hetero phenanthrene-10-oxide derivative is suc as formula shown in the II,
But the preparation reference literature of this compound (Polymer, 39,5819-5826,1998) etc. is prepared, by starting raw material orthoxenol derivative with the phosphorus trichloride condensation remove hydrogenchloride be hydrolyzed again and dewater after obtain.
The chemical structural formula of siloxanes that contains two carbon-carbon double bonds is shown in formula III:
But the preparation reference literature of this compound (polymer material science and engineering 2000 the 16th volume 3 phase 67-69) is prepared, and is blended in certain proportion by alkyl divinyl disiloxane derivative and alkyl cyclotetrasiloxane and carries out balanced reaction under the alkali existence condition and obtain.
The present invention will be described in detail technical scheme of the present invention by following specific embodiment, but the present invention is not limited to embodiment proposed below.
Embodiment 1:
With 216g (1mol) 9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 93g (0.5mol) 1; 1; 2; 2-tetramethyl--1; the 2-divinyl disiloxane adds in the 500mL there-necked flask, adds the tetrahydrofuran solution that 5-6 drips the 25mmol/L Platinic chloride, heated and stirred reaction under nitrogen protection.Controlled temperature is a reflux temperature, temperature rises after refluxing about 8 hours, controlled temperature be 160 ℃ of reactions after 12 hours underpressure distillation remove the lower-boiling impurity that generates in the dereaction, cool to 60 ℃, wash the impurity that generates in 3 ~ 5 flush away reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains faint yellow transparent solid (compound one).
Fig. 1 is the nucleus magnetic hydrogen spectrum spectrogram of compound one; Fig. 2 is its MALDI-TOF mass spectrum, and the result represents very purified product.All the other embodiment compounds confirm all that through nucleus magnetic hydrogen spectrum and mass spectroscopy the gained compound structure is correct, and the validity of synthetic method of the present invention has been described.
Embodiment 2:
With 216g (1mol) 9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 155g (0.5mol) 1; 2-dimethyl-1; 2-phenylbenzene-1; the 2-divinyl disiloxane adds in the 500mL there-necked flask; the ethanolic soln that adds 5 ~ 6 25mmol/L Palladous chlorides, heated and stirred reaction under nitrogen protection.About 150 ℃ of controlled temperature, react underpressure distillation after 72 hours and remove the lower-boiling impurity that generates in the dereaction, cool to 60 ℃, wash the low polar impurity that generates in 3 ~ 5 flush awaies reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains faint yellow transparent solid (compound two).
Embodiment 3:
With 216g (1mol) 9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 217g (0.5mol) 1; 1; 2; 2-tetraphenyl-1; the 2-divinyl disiloxane adds in the 500mL there-necked flask, adds the dioxane solution of 5 ~ 6 25mmol/L rhodium chlorides, heated and stirred reaction under nitrogen protection.About 150 ℃ of controlled temperature, react underpressure distillation after 24 hours and remove the lower-boiling impurity that generates in the dereaction, cool to 60 ℃, wash the low polar impurity that generates in 3 ~ 5 flush awaies reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains faint yellow transparent solid (compound three).
Embodiment 4:
With 216g (1mol) 9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 93g (0.5mol) 1,1; 2,2-tetramethyl--1,2-divinyl disiloxane add in the 500mL there-necked flask; add 16.4g radical initiator AIBN and 100mL benzene, heated and stirred reaction under nitrogen protection.Controlled temperature is 80 ℃, back flow reaction after 12 hours underpressure distillation remove desolvate and react in the lower-boiling impurity that generates, cool to 60 ℃, wash the low polar impurity that generates in 3 ~ 5 flush away reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains the faint yellow transparent solid of faint yellow transparent solid (compound one).
Embodiment 5:
With 216g (1mol) 9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 155g (0.5mol) 1; 2-dimethyl-1; 2-phenylbenzene-1; the 2-divinyl disiloxane adds in the 500mL there-necked flask; add 20g radical initiator ABVN and 100mL toluene, heated and stirred reaction under nitrogen protection.Controlled temperature is 80 ℃, back flow reaction after 1 hour underpressure distillation remove desolvate and react in the lower-boiling impurity that generates, cool to 60 ℃, wash the low polar impurity that generates in 3 ~ 5 flush away reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains the faint yellow transparent solid of faint yellow transparent solid (compound two).
Embodiment 6:
With 216g (1mol) 9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 217g (0.5mol) 1; 1; 2; 2-tetraphenyl-1; the 2-divinyl disiloxane adds in the 500mL there-necked flask, adds 20g radical initiator BP0 and 100mL tetrahydrofuran (THF), heated and stirred reaction under nitrogen protection.Controlled temperature is 60 ℃, back flow reaction after 12 hours underpressure distillation remove desolvate and react in the lower-boiling impurity that generates, wash the low polar impurity that generates in 3 ~ 5 flush away reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains the faint yellow transparent solid of faint yellow transparent solid (compound three).
Embodiment 7:
With 230g (1mol) 3-methyl-9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 93g (0.5mol) 1; 1; 2; 2-tetramethyl--1; the 2-divinyl disiloxane adds in the 500mL there-necked flask, adds the tetrahydrofuran solution of 5 ~ 6 25mmol/L Platinic chlorides three (triphenyl phosphorus) title complex, heated and stirred reaction under nitrogen protection.Controlled temperature be 160 ℃ of reactions after 12 hours underpressure distillation remove the lower-boiling impurity that generates in the dereaction, cool to 60 ℃, wash the impurity that generates in 3 ~ 5 flush away reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains faint yellow transparent solid (compound four).
Embodiment 8:
With 244g (1mol) 3-ethyl-9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 155g (0.5mol) 1; 2-dimethyl-1; 2-phenylbenzene-1; the 2-divinyl disiloxane adds in the 500mL there-necked flask; the ethanolic soln that adds 5 ~ 6 25mmol/L Palladous chlorides three (triphenyl phosphorus) title complex, heated and stirred reaction under nitrogen protection.About 150 ℃ of controlled temperature, react underpressure distillation after 24 hours and remove the lower-boiling impurity that generates in the dereaction, cool to 60 ℃, wash the low polar impurity that generates in 3 ~ 5 flush awaies reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains faint yellow transparent solid (compound five).
Embodiment 9:
With 293g (1mol) 3-phenyl-9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 217g (0.5mol) 1; 1; 2; 2-tetraphenyl-1; the 2-divinyl disiloxane adds in the 500mL there-necked flask, adds the dioxane solution of 5 ~ 6 25mmol/L rhodium chlorides three (triphenyl phosphorus) title complex, heated and stirred reaction under nitrogen protection.About 150 ℃ of controlled temperature, react underpressure distillation after 24 hours and remove the lower-boiling impurity that generates in the dereaction, cool to 60 ℃, wash the low polar impurity that generates in 3 ~ 5 flush awaies reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains faint yellow transparent solid (compound six).
Embodiment 10:
With 244g (1mol) 3; 6-dimethyl-9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 130g (0.5mol) 1,1,2; 2; 3,3-vegolysen, 3-divinyl trisiloxanes add in the 500mL there-necked flask; add 20g radical initiator dicumyl peroxide and 100mL benzene, heated and stirred reaction under nitrogen protection.Controlled temperature is 80 ℃, back flow reaction after 12 hours underpressure distillation remove desolvate and react in the lower-boiling impurity that generates, cool to 60 ℃, wash the low polar impurity that generates in 3 ~ 5 flush away reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains the faint yellow transparent solid of faint yellow transparent solid (compound seven).
Embodiment 11:
With 272g (1mol) 3; 6-diethyl-9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 161g (0.5mol) 1; 2,3-trimethylammonium-1,2; 3-triphenyl-1; the 3-divinyl disiloxane adds in the 500mL there-necked flask, adds 20g radical initiator di-tert-butyl peroxide and 100mL toluene, heated and stirred reaction under nitrogen protection.Controlled temperature is 80 ℃, back flow reaction after 12 hours underpressure distillation remove desolvate and react in the lower-boiling impurity that generates, cool to 60 ℃, wash the low polar impurity that generates in 3 ~ 5 flush away reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains the faint yellow transparent solid of faint yellow transparent solid (compound eight).
Embodiment 12:
With 272g (1mol) 1; 2; 3,4-tetramethyl--9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 107g (0.5mol) 1; 1; 2,2-tetramethyl--1,2-diallyl sily oxide add in the 500mL there-necked flask; add 20g radical initiator dilauroyl peroxide and 100mL ethanol, heated and stirred reaction under nitrogen protection.Controlled temperature is 60 ℃, back flow reaction after 12 hours underpressure distillation remove desolvate and react in the lower-boiling impurity that generates, wash the low polar impurity that generates in 3 ~ 5 flush away reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains the faint yellow transparent solid of faint yellow transparent solid (compound nine).
Embodiment 13:
With 293g (1mol) 2-phenyl-9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 138g (0.5mol) 1,1,2; 2; 3,3-vegolysen, 3-diallyl trisiloxanes add in the 500mL there-necked flask; the tetrahydrofuran solution that adds 5 ~ 6 25mmol/L Platinic chlorides three (triethoxy phosphine) title complex; controlled temperature is a reflux temperature, and temperature rises after refluxing about 8 hours, heated and stirred reaction under nitrogen protection.Controlled temperature be 160 ℃ of reactions after 12 hours underpressure distillation remove the lower-boiling impurity that generates in the dereaction, cool to 60 ℃, wash the impurity that generates in 3 ~ 5 flush away reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains faint yellow transparent solid (compound ten).
Embodiment 14:
With 258g (1mol) 4-propyl group-9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 169g (0.5mol) 1; 2-dimethyl-1; 2-phenylbenzene-1; 2-diallyl sily oxide adds in the 500mL there-necked flask; the ethanolic soln that adds 5 ~ 6 25mmol/L Palladous chlorides three (triethoxy phosphine) title complex, heated and stirred reaction under nitrogen protection.About 150 ℃ of controlled temperature, react underpressure distillation after 24 hours and remove the lower-boiling impurity that generates in the dereaction, cool to 60 ℃, wash the low polar impurity that generates in 3 ~ 5 flush awaies reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains faint yellow transparent solid (compound 11).
Embodiment 15:
With 216g (1mol) 3-methoxyl group-9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 217g (0.5mol) 1; 1; 2; 2-tetraphenyl-1; the 2-divinyl disiloxane adds in the 500mL there-necked flask, adds the dioxane solution of 5 ~ 6 25mmol/L rhodium chlorides three (triethoxy phosphine) title complex, heated and stirred reaction under nitrogen protection.About 150 ℃ of controlled temperature, react underpressure distillation after 24 hours and remove the lower-boiling impurity that generates in the dereaction, cool to 60 ℃, wash the low polar impurity that generates in 3 ~ 5 flush awaies reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains faint yellow transparent solid (compound 12).
Embodiment 16:
With 216g (1mol) 3-benzyl-9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 121g (0.5mol) 1; 1; 2; 2-tetramethyl--1; 2-dibutene base sily oxide adds in the 500mL there-necked flask, adds special butyl ester of 16.4g radical initiator peroxidation phenylformic acid and 100mL benzene, heated and stirred reaction under nitrogen protection.Controlled temperature is 80 ℃, back flow reaction after 12 hours underpressure distillation remove desolvate and react in the lower-boiling impurity that generates, cool to 60 ℃, wash the low polar impurity that generates in 3 ~ 5 flush away reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains the faint yellow transparent solid of faint yellow transparent solid (compound 13).
Embodiment 17:
With 272g (1mol) 5,6,7; 8-tetramethyl--9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 167g (0.5mol) 1,1; 2,2,3; 3; 4,4-prestox-1,4-divinyl tetrasiloxane add in the 500mL there-necked flask; add 20g radical initiator peroxide tert pivalate ester and 100mL toluene, heated and stirred reaction under nitrogen protection.Controlled temperature is 80 ℃, back flow reaction after 12 hours underpressure distillation remove desolvate and react in the lower-boiling impurity that generates, cool to 60 ℃, wash the low polar impurity that generates in 3 ~ 5 flush away reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains faint yellow transparent solid (compound 14).
Embodiment 18:
With 284g (1mol) 4-trifluoromethyl-9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 231g (0.5mol) 1; 1; 2; 2-tetraphenyl-1; 2-diallyl sily oxide adds in the 500mL there-necked flask, adds 20g radical initiator di-cyclohexylperoxy dicarbonate and 100mL ethanol, heated and stirred reaction under nitrogen protection.Controlled temperature is 60 ℃, back flow reaction after 12 hours underpressure distillation remove desolvate and react in the lower-boiling impurity that generates, wash the low polar impurity that generates in 3 ~ 5 flush away reactions with sherwood oil, underpressure distillation removes the postcooling that desolvates, and obtains faint yellow transparent solid (compound 15).
Embodiment 19:
Will be by compound one 20g, linear phenolic resin (Phenol novolac) (TD-2131,70 ℃ of softening temperatures, hydroxyl equivalent 105g/mol, Dainippon Ink ﹠amp; Chemicals Inc.) 28g, linear phenolic epoxy resin (Phenolnovolac epoxy) (195LL, 65 ℃ of softening temperatures, epoxy equivalent (weight) 195g/mol, Yuka Shell Epoxy KK) it is even that 52g, 0.5g triphenyl phosphorus are heated to 120 ℃ of melting mixing, casting mold after the deaeration, 150 ℃ solidified 3 hours, and 180 ℃ of after fixing 2 hours obtain the fire retarding epoxide resin of excellent combination property.Its tensile strength is 97MPa, and elongation at break is 5.4%, and flexural strength is 152MPa, and flame retardant properties reaches UL94 V-0 level.
Embodiment 20:
With compound two 25g, linear phenolic resin (Phenol novolac) (TD-2131,70 ℃ of softening temperatures, hydroxyl equivalent 105g/mol, Dainippon Ink ﹠amp; Chemicals Inc.) 26g, linear phenolic epoxy resin (Phenolnovolac epoxy) (195LL, 65 ℃ of softening temperatures, epoxy equivalent (weight) 195g/mol, Yuka Shell Epoxy KK) it is even that 49g, 0.5g triphenyl phosphorus are heated to 120 ℃ of melting mixing, casting mold after the deaeration, 150 ℃ solidified 3 hours, and 180 ℃ of after fixing 2 hours obtain the fire retarding epoxide resin of excellent combination property.Its tensile strength is 96MPa, and elongation at break is 4.5%, and flexural strength is 161MPa, and flame retardant properties reaches UL94 V-0 level.
Embodiment 21:
With compound three 30g, linear phenolic resin (Phenol novolac) (TD-2131,70 ℃ of softening temperatures, hydroxyl equivalent 105g/mol, Dainippon Ink ﹠amp; Chemicals Inc.) 50g, hexamethylenetetramine 15g heating mixes, and obtains flame retardant level UL94 V-0 level behind the completion of cure, the resin of mechanical property excellence.
Embodiment 22:
With compound four 30g, mix behind the polycarbonate 90g heating and melting, test bars is processed in injection molding, and the back test that polishes flat obtains flame retardant level UL94 V-0 level, the resin of mechanical property excellence.
Embodiment 23:
With compound five 30g, mix behind the polybutylene terephthalate 90g heating and melting, test bars is processed in injection molding, and the back test that polishes flat obtains flame retardant level UL94 V-0 level, the resin of mechanical property excellence.
Embodiment 24:
With compound six 30g, mix behind the polyethylene terephthalate 90g heating and melting, test bars is processed in injection molding, and the back test that polishes flat obtains flame retardant level UL94 V-0 level, the resin of mechanical property excellence.
Embodiment 25:
With compound seven 30g, mix behind the polysulfones 90g heating and melting, test bars is processed in injection molding, and the back test that polishes flat obtains flame retardant level UL94 V-0 level, the resin of mechanical property excellence.
Embodiment 26:
With compound eight 30g, mix behind the polyphenylene oxide 80g heating and melting, test bars is processed in injection molding, and the back test that polishes flat obtains flame retardant level UL94 V-0 level, the resin of mechanical property excellence.
Embodiment 27:
With compound nine 30g, mix behind the polymeric amide 90g heating and melting, test bars is processed in injection molding, and the back test that polishes flat obtains flame retardant level UL94 V-0 level, the resin of mechanical property excellence.
Embodiment 28:
With compound ten 30g, mix behind the polystyrene 70g heating and melting, test bars is processed in injection molding, and the back test that polishes flat obtains flame retardant level UL94 V-0 level, the resin of mechanical property excellence.
Embodiment 29:
With compound 11 30g, linear phenolic resin (Phenol novolac) (TD-2131,70 ℃ of softening temperatures, hydroxyl equivalent 105g/mol, Dainippon Ink ﹠amp; Chemicals Inc.) 28g, linear phenolic epoxy resin (Phenolnovolac epoxy) (195LL, 65 ℃ of softening temperatures, epoxy equivalent (weight) 195g/mol, Yuka Shell Epoxy KK) it is even that 52g, 0.5g triphenyl phosphorus are heated to 120 ℃ of melting mixing, casting mold after the deaeration, 150 ℃ solidified 3 hours, and 180 ℃ of after fixing 2 hours obtain the fire retarding epoxide resin of excellent combination property.
Embodiment 30:
With compound 12 30g, mix behind the polyvinyl chloride 90g heating and melting, test bars is processed in injection molding, and the back test that polishes flat obtains flame retardant level UL94 V-0 level, the resin of mechanical property excellence.
Embodiment 31:
With compound 13 30g, mix behind the polymethylmethacrylate 90g heating and melting, test bars is processed in injection molding, and the back test that polishes flat obtains flame retardant level UL94 V-0 level, the resin of mechanical property excellence.
Embodiment 32:
With compound 14 30g, mix behind the polyphenylene sulfide 90g heating and melting, test bars is processed in injection molding, and the back test that polishes flat obtains flame retardant level UL94 V-0 level, the resin of mechanical property excellence.
Embodiment 33:
With compound 15 30g, mix behind the PC/ABS alloy 70g heating and melting, test bars is processed in injection molding, and the back test that polishes flat obtains flame retardant level UL94 V-0 level, the resin of mechanical property excellence.
Comparative Examples 1:
With linear phenolic resin (Phenol novolac) (TD-2131,70 ℃ of softening temperatures, hydroxyl equivalent 105g/mol, Dainippon Ink ﹠amp; Chemicals Inc.) 35g, linear phenolic epoxy resin (Phenol novolac epoxy) (195LL, 65 ℃ of softening temperatures, epoxy equivalent (weight) 195g/mol, Yuka Shell Epoxy KK) it is even that 65g, 0.65g triphenyl phosphorus are heated to 120 ℃ of melting mixing, casting mold after the deaeration, 150 ℃ solidified 3 hours, and 180 ℃ of after fixing 2 hours obtain not fire-retardant toughened epoxy resin cured product.Its tensile strength is 68MPa, and elongation at break is 3.4%, and flexural strength is 127MPa, and flame retardant resistance is a UL94 not V-2 level.
Comparative example 19-33 and Comparative Examples 1, result show that organic silicon compound containing phosphorus of the present invention makes this macromolecular material have extraordinary flame retardant properties after adding macromolecular material with certain proportion.
Claims (13)
1. the organic silicon compound containing phosphorus of formula I structure,
Wherein, R
1, R
2, R
3, R
4Be selected from aryl, aryloxy that alkoxyl group, aryl, the halogen of alkyl, the C1-C5 of C1-C5 replace; R
5With R
6Alkylidene group for C0-C5; R
7-R
14Be selected from aryl, aryloxy that alkyl, nitro, the alkoxyl group of C1-C5, aryl, the halogen of hydrogen atom, C1-C5 replace; N is 1-10.
2. organic silicon compound containing phosphorus according to claim 1 is characterized in that: R
1, R
2, R
3, R
4Be selected from methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-, phenyl and phenoxy group.
3. organic silicon compound containing phosphorus according to claim 1 is characterized in that: R
5With R
6Be selected from methylene radical, ethylidene, propylidene and butylidene.
4. organic silicon compound containing phosphorus according to claim 1 is characterized in that: R
7-R
14Be selected from hydrogen atom, methyl, ethyl, propyl group, nitro, methoxyl group, oxyethyl group, propoxy-, phenyl and phenoxy group.
5. organic silicon compound containing phosphorus according to claim 1 is characterized in that: n is 1-4.
6. the preparation method of the organic silicon compound containing phosphorus of the described formula I structure of claim 1, be under catalyzer or action of free radical initiator, by 9 of formula II structure, the 10-dihydro-9-oxy is assorted-and the siloxanes of 10-phospho hetero phenanthrene-10-oxide derivative and formula III structure reacts, and obtains the organic silicon compound containing phosphorus of described formula I structure;
(formula III)
Wherein, R
1, R
2, R
3, R
4Be selected from aryl, aryloxy that alkoxyl group, aryl, the halogen of alkyl, the C1-C5 of C1-C5 replace; R
5With R
6Alkylidene group for C0-C5; R
7-R
14Be selected from aryl, aryloxy that alkyl, nitro, the alkoxyl group of C1-C5, aryl, the halogen of hydrogen atom, C1-C5 replace; N is 1-10.
7. preparation method according to claim 6 is characterized in that: 9 of formula II structure, and the 10-dihydro-9-oxy is assorted-and the weight ratio of the siloxanes of 10-phospho hetero phenanthrene-10-oxide derivative and formula III structure is 100: 1-400.
8. according to claim 6 or 7 described preparation methods, it is characterized in that: described catalyzer is selected from Platinic chloride, palladium chloride, Trichlororhodium, perhaps, and the title complex of Platinic chloride, palladium chloride, Trichlororhodium.
9. preparation method according to claim 8 is characterized in that: the title complex of Platinic chloride, palladium chloride, Trichlororhodium is X (PPh
3)
3Cl, X (PPh
3)
3Cl
2, X (PPh
3)
3Cl
3, X (POEt
3)
3Cl, X (POEt
3)
3H
2(CO), X represents platinum, palladium and rhodium.
10. according to claim 6 or 7 described preparation methods, it is characterized in that: described radical initiator comprises one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), hydrogen peroxide, isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, the special butyl ester of peroxidation phenylformic acid, peroxide tert pivalate ester, peroxy dicarbonate diisobutyl ester, di-cyclohexylperoxy dicarbonate, Potassium Persulphate, the ammonium persulphate.
11. according to claim 6 or 7 described preparation methods, it is characterized in that: the solvent of reaction comprises methyl alcohol, ethanol, propyl alcohol, Virahol, benzene,toluene,xylene, trimethylbenzene, chlorobenzene, oil of mirbane, hexone, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, methyl tertbutyl ketone, methyl acetate, ethyl acetate, butylacetate, acetate glycidyl ester, tetrahydrofuran (THF), dioxane, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide and the mixture that mixes by arbitrary proportion thereof.
12. according to claim 6 or 7 described preparation methods, it is characterized in that: temperature of reaction is 30-180 ℃; Reaction times is 1-72 hour.
13. the organic silicon compound containing phosphorus of the described formula I structure of claim 1 is as the application of the fire retardant of macromolecular material.
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