CN105461931A - Hyperbranched polysiloxane, and preparation method and composition thereof - Google Patents
Hyperbranched polysiloxane, and preparation method and composition thereof Download PDFInfo
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- CN105461931A CN105461931A CN201510995820.3A CN201510995820A CN105461931A CN 105461931 A CN105461931 A CN 105461931A CN 201510995820 A CN201510995820 A CN 201510995820A CN 105461931 A CN105461931 A CN 105461931A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a hyperbranched polysiloxane, and a preparation method and composition thereof. The preparation method comprises the following steps: adding epoxy siloxane and 9,10-dihydro-9-oxa-10-phosphaphenanthrene--10-oxide into a reactor which is provided with a stirrer, a thermometer and a reflux condensation tube, and stirring at 25-60 DEG C for 30 minutes; adding triphenylphosphine, and reacting at 100-120 DEG C for 8 hours while stirring; cooling to 60 DEG C, adding methoxy siloxane, water and ammonia water into a three-necked bottle, and stirring to react for 4.5 hours; and finally, adding a proper amount of 1-chlorotrimethylsilane, and reacting for 1 hour to obtain the orange thick liquid product phosphorus-containing hyperbranched polysiloxane. The phosphorus-containing hyperbranched polysiloxane is used as an epoxy resin curing system flame retardant, has favorable compatibility, and enhances the flame-retardant effect by utilizing the synergistic effect between phosphorus and silicon.
Description
Technical field
The present invention relates to fire retardant in a kind of engineering plastics, relate to a kind of organic silicon resin fire retardant in particular, the invention still further relates to a kind of preparation method of organic silicon resin fire retardant and the composition containing organic silicon resin fire retardant thereof.
Background technology
Have employed a large amount of fire retardants during engineering plastics are shaping, as halogen contained compound, boron derivative, metal oxide, P contained compound etc., can singly to add or composite.But fire retardant material that is chloride and bromine is easily released when burning has pungency and corrosive hydrogen halide, and halogen flame is restricted gradually; In order to avoid the harm using traditional halogenated flame retardant to bring environment, people are devoted to develop halogen-free flame retardants now.Conventional phosphorous, compound that nitrogen class is fire-retardant, can cause ecological problem again.In recent years, utilize the synergistic effect between phosphorus silicon fire retardant, prepare phosphorus silicon and work in coordination with combustion-supporting system to improve the favor that epoxy resin is subject to scientist.When phosphorus silicon fire retardant uses, under high-temp combustion, phosphorus catalyzed reaction can become charcoal, and silicon works the thermostability increasing the layer of charcoal generated, and plays the cooperative flame retardant effect of phosphorus silicon.And when banning silane with siloxanes, the flame retardant effect meeting reinforcement further that phosphorus silicon is collaborative, because siloxanes can react generate SiO
2protective layer, stops the oxidation of layer of charcoal, makes layer of charcoal more stable.
The people such as plastics industry open Zhang Lili in 2005 utilize 1-oxo-1-phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclo octane (PEPA) and Nano-meter SiO_2
2add epoxy resin research to, find PEPA and SiO2 under Different adding amount flame retardant effect great changes have taken place, the LOI of epoxy resin and the massfraction of phosphorus silicon have certain linear relationship, and this just illustrates that the cooperative flame retardant between phosphorus silicon can improve the flame retardant resistance of epoxy resin well.When PEPA is used alone, the massfraction of phosphoric is before 2.58%, and the LOI of epoxy resin can have with the content of phosphorus to be increased faster.But when the massfraction of phosphoric is 2.58% to 3.44% time, the LOI of epoxy resin is substantially constant, merely add 1%.When using together with PEPA with SiO2, phosphorus content is 3.44% and silicone content when being 0.93%, and add 1.5 when the relative PEPA of LOI of epoxy resin is used alone, this just illustrates, the synergistic effect of phosphorus silicon can increase flame retardant effect.Meanwhile, they are by combustion testing, find that the layer of charcoal of phosphorus silicon synergistic fire retardant occurs quicker comparatively speaking, and the heat decomposition temperature of epoxy resin are much high comparatively speaking.Finally, test PEPA and SiO2 is elevated to 26.5 by what change that addition makes the oxygen index of epoxy resin by 19.8, vertical combustion can reach UL94V-0 level.
Summary of the invention
The object of this invention is to provide a kind of hyperbranched polyorganosiloxane, as fire retardant, reach phosphorus silicon cooperative flame retardant, to improve flame retardant effect by phosphorous and silicon group wherein.
Another object of the present invention is to provide a kind of preparation method of hyperbranched polyorganosiloxane.
Of the present invention also have an object to be to provide a kind of composition comprising hyperbranched polyorganosiloxane.
A kind of hyperbranched polyorganosiloxane of the present invention, structural formula is as shown in (I):
The preparation method of hyperbranched polyorganosiloxane hyperbranched polyorganosiloxane of the present invention:
A. the siloxanes of epoxy group(ing) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are put into and agitator are installed, reactor that temperature takes into account reflux condensing tube, stir 30 minutes at 25 ~ 60 DEG C;
B. then triphenylphosphine is added, stirring reaction 8 hours at 100 DEG C-120 DEG C;
C. temperature is reduced to the siloxanes, the water that add methoxyl group in 60 DEG C of backward three-necked bottles, and ammoniacal liquor, stirring reaction 4.5 hours;
D. finally adding appropriate 1-chlorine trimethyl silane again reacts 1 hour, after end, products therefrom is placed in the beaker precipitated and separated that normal hexane is housed, collect lower floor's solution and remove unreacted material, lower floor's solution is carried out revolving steaming, until inclusion-free steams, finally obtain orange-yellow thick liquid product.
The preparation method of hyperbranched polyorganosiloxane of the present invention, wherein, the molar ratio 1:1 ~ 1:1.5 of the siloxanes of epoxy group(ing) and the siloxanes of methoxyl group.The preparation method of hyperbranched polyorganosiloxane of the present invention, wherein, the ratio 1:0.5 ~ 1:1 of the siloxanes of epoxy group(ing) and the siloxanes of methoxyl group and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
The preparation method of hyperbranched polyorganosiloxane of the present invention, wherein, the siloxanes of described epoxy group(ing) is γ-glycidyl ether oxygen propyl trimethoxy silicane.
The preparation method of hyperbranched polyorganosiloxane of the present invention, wherein, the siloxanes of methoxyl group is dimethyldimethoxysil,ne.
A kind of composition comprising hyperbranched polyorganosiloxane of the present invention, mainly consists of: with weight parts,
Epoxy resin 100 weight part,
Hyperbranched polyorganosiloxane 8.5-80 weight part,
4,4-diaminodiphenyl-methane 20 weight part.
The composition of hyperbranched polyorganosiloxane of the present invention, wherein, epoxy resin is Racemic glycidol ethers, aromatic series or aliphatic epoxy resin.
The composition of hyperbranched polyorganosiloxane of the present invention, wherein, epoxy resin is novolac epoxy.
The present invention has following beneficial effect:
Hyperbranched polyorganosiloxane of the present invention, as fire retardant, can improve ethoxyline resin antiflaming, and very good with the consistency of epoxy resin.Hyperbranched polyorganosiloxane is orange-yellow transparent liquid at normal temperatures, is easy to mix with epoxy resin, is applicable to the overwhelming majority and plants based epoxy resin, by the homogeneous bubble-free of epoxy resin casting matrix that it is fire-retardant.
The phosphorus silicon group that hyperbranched polyorganosiloxane of the present invention contains, the synergistic effect between phosphorus silicon, strengthens flame retardant effect.
Accompanying drawing explanation
The structural formula of Fig. 1 hyperbranched polyorganosiloxane of the present invention.
The FTIR spectrum of each reaction times section at Fig. 2 reactant of the present invention 120 DEG C.
The infrared figure of Fig. 3 hyperbranched polyorganosiloxane of the present invention.
Embodiment
By the following examples the present invention is further described specifically.What be necessary to herein means out is that following examples are only for the present invention is described further; limiting the scope of the invention can not be interpreted as; this art skilled person makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection scope of the present invention.
Embodiment 1
By 10.3g (0.05mol) γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560, Zhonglan Chenguang Chemical Inst) and 10.75g (0.05mol) 9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (DOPO, Chengdu Ke Long chemical reagent factory) be dissolved in 40ml dimethylbenzene put into agitator is installed, 250ml round bottom three-necked bottle that temperature takes into account reflux condensing tube, stir 30 minutes in the waters pot of certain temperature.Then in three-necked bottle, add the triphenylphosphine (Chengdu Ke Long chemical reagent factory) of 0.316g.Stirring reaction 8 hours at 120 DEG C.
Temperature is reduced in 60 DEG C of backward three-necked bottles and adds (0.075mol) 9g dimethyldimethoxysil,ne (DEMS, Chengdu Ke Long chemical reagent factory), 3.78g water, with 0.3g and ammoniacal liquor, stirring reaction 4.5 hours, finally adds appropriate 1-chlorine trimethyl silane again and reacts 1 hour.After end, products therefrom is placed in the beaker precipitated and separated that normal hexane is housed, collects lower floor's solution and remove unreacted material.Lower floor's solution is carried out revolving steaming, until inclusion-free steams, finally obtains orange-yellow thick liquid, preserve stand-by.Adopt determination of ubbelohde viscometer limiting viscosity, dehydrated alcohol is as solvent.Getting appropriate polymkeric substance is dissolved in 25ml ethanol solution, measures synthesis silicone resin viscosity in 25 DEG C of constant temperature waters.
By the FTIR spectrum of reactant DOPO and KH560 each reaction times section at 120 DEG C.2436cm
-1absorption peak corresponding be the absorption peak of P-H in DOPO, 910cm
-1absorption peak corresponding be the absorption peak of KH560 epoxy group.2436cm in collection of illustrative plates
-1peak reduce along with the increase peak area in reaction times, carry out postpeak completely dissolve in 2 hours in reaction; 910cm
-1peak also disappear along with the increase in reaction times, carry out the basic completely dissolve of postpeak in 2 hours in reaction equally.This just can determine that P-H and epoxy group(ing) there occurs reaction, and reacts completely after 2 hours.
From the FTIR spectrum figure of hyperbranched polyorganosiloxane, 1036cm can be seen
-1and 1165cm
-1between strong and wide absorption band be Si-O-Si antisymmetric stretching vibration peak.3398cm
-1the absorption peak of the peak Si-OH occurred.1198cm
-1peak be the absorption peak of P=O.1260cm
-1the absorption peak of absorption peak C-O-C.The absorption peak of P=O and C-O-C simultaneously occurred from figure and the 2436cm of disappearance
-1and 910cm
-1absorption peak, show the addition reaction that there occurs P=O and epoxy group(ing) between DOPO and KH560.By the absorption peak of the Si-O-Si antisymmetric stretching vibration peak that occurs in product and Si-OH, determine hydrolysis reaction also success.
Embodiment 2
By 10.3g (0.05mol) γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560, Zhonglan Chenguang Chemical Inst) and 5.275g (0.025mol) 9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (DOPO, Chengdu Ke Long chemical reagent factory) be dissolved in 40ml dimethylbenzene put into agitator is installed, 250ml round bottom three-necked bottle that temperature takes into account reflux condensing tube, stir 30 minutes in the waters pot of certain temperature.Then in three-necked bottle, add the triphenylphosphine (Chengdu Ke Long chemical reagent factory) of 0.234g.Stirring reaction 8 hours at 100 DEG C-120 DEG C.
Temperature is reduced in 60 DEG C of backward three-necked bottles and adds (0.075mol) 9g dimethyldimethoxysil,ne (DEMS, Chengdu Ke Long chemical reagent factory), 3.78g water, with 0.3g and ammoniacal liquor, stirring reaction 4.5 hours, finally adds appropriate 1-chlorine trimethyl silane again and reacts 1 hour.After end, products therefrom is placed in the beaker precipitated and separated that normal hexane is housed, collects lower floor's solution and remove unreacted material.Lower floor's solution is carried out revolving steaming, until inclusion-free steams, finally obtains orange-yellow thick liquid, preserve stand-by.Adopt determination of ubbelohde viscometer limiting viscosity, dehydrated alcohol is as solvent.Getting appropriate polymkeric substance is dissolved in 25ml ethanol solution, measures synthesis silicone resin viscosity in 25 DEG C of constant temperature waters.
Embodiment 3
The synthesis of hyperbranched polyorganosiloxane: by 10.3g (0.05mol) γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560, Zhonglan Chenguang Chemical Inst) and 10.75g (0.05mol) 9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (DOPO, Chengdu Ke Long chemical reagent factory) put into agitator is installed, 250ml round bottom three-necked bottle that temperature takes into account reflux condensing tube, stir 30 minutes in the waters pot of certain temperature.Then in three-necked bottle, add the triphenylphosphine (Chengdu Ke Long chemical reagent factory) of 0.316g.Stirring reaction 8 hours at 120 DEG C.
Temperature is reduced in 60 DEG C of backward three-necked bottles and adds 7.2g (0.06mol) dimethyldimethoxysil,ne (DEMS, Chengdu Ke Long chemical reagent factory), 2.42g water, and 0.3g ammoniacal liquor, stirring reaction 4.5 hours, finally adds appropriate 1-chlorine trimethyl silane (Chengdu Ke Long chemical reagent factory) again and reacts 1 hour.After end, products therefrom is placed in the beaker precipitated and separated that normal hexane is housed, collects lower floor's solution and remove unreacted material.Lower floor's solution is carried out revolving steaming, until inclusion-free steams, finally obtains orange-yellow thick liquid, preserve stand-by.
Embodiment 4
Composition epoxy resin: by the hyperbranched polyorganosiloxane 8.5 parts of example 1, novolac epoxy (oxirane value 0.51mol/100g, Shanghai resin company limited F51) 100 parts, 4,4-diaminodiphenyl-methane (DDM, Chengdu Ke Long chemical reagent factory) 20 parts, make it dissolve, to be mixed evenly after, be poured into (for preventing silicone resin from solidifying, this step must complete in 15 minutes) in the mould of preheating.Then be heating and curing in the air dry oven of optimal temperature, temperature is 80 DEG C/2 hours, 120 DEG C/2 hours, 160 DEG C/2 hours. namely obtain fire-retardant epoxy resin fat cured article after solidification.
Embodiment 5
Composition epoxy resin: by hyperbranched polyorganosiloxane 25 parts, novolac epoxy (oxirane value 0.51mol/100g, Shanghai resin company limited F51) 100 parts, 4,4-diaminodiphenyl-methane (DDM, Chengdu Ke Long chemical reagent factory) 20 parts, make it dissolve, to be mixed evenly after, be poured into (for preventing silicone resin from solidifying, this step must complete in 15 minutes) in the mould of preheating.Then be heating and curing in the air dry oven of optimal temperature, temperature is 80 DEG C/2 hours, 120 DEG C/2 hours, 160 DEG C/2 hours. namely obtain fire-retardant epoxy resin fat cured article after solidification.
Embodiment 6
Composition epoxy resin: by hyperbranched polyorganosiloxane 30 parts, novolac epoxy (oxirane value 0.51mol/100g, Shanghai resin company limited F51) 100 parts, 4,4-diaminodiphenyl-methane (DDM, Chengdu Ke Long chemical reagent factory) 20 parts, make it dissolve, to be mixed evenly after, be poured into (for preventing silicone resin from solidifying, this step must complete in 15 minutes) in the mould of preheating.Then be heating and curing in the air dry oven of optimal temperature, temperature is 80 DEG C/2 hours, 120 DEG C/2 hours, 160 DEG C/2 hours. namely obtain fire-retardant epoxy resin fat cured article after solidification.
Embodiment 7
Composition epoxy resin: by the hyperbranched polyorganosiloxane 35 parts of example 1, novolac epoxy (oxirane value 0.51mol/100g, Shanghai resin company limited F51) 100 parts, 4,4-diaminodiphenyl-methane (DDM, Chengdu Ke Long chemical reagent factory) 20 parts, make it dissolve, to be mixed evenly after, be poured into (for preventing silicone resin from solidifying, this step must complete in 15 minutes) in the mould of preheating.Then be heating and curing in the air dry oven of optimal temperature, temperature is 80 DEG C/2 hours, 120 DEG C/2 hours, 160 DEG C/2 hours. namely obtain fire-retardant epoxy resin fat cured article after solidification.
Embodiment 8
Composition epoxy resin: by the hyperbranched polyorganosiloxane 40 parts of example 1, novolac epoxy (oxirane value 0.51mol/100g, Shanghai resin company limited F51) 100 parts, 4,4-diaminodiphenyl-methane (DDM, Chengdu Ke Long chemical reagent factory) 20 parts, make it dissolve, to be mixed evenly after, be poured into (for preventing silicone resin from solidifying, this step must complete in 15 minutes) in the mould of preheating.Then be heating and curing in the air dry oven of optimal temperature, temperature is 80 DEG C/2 hours, 120 DEG C/2 hours, 160 DEG C/2 hours. namely obtain fire-retardant epoxy resin fat cured article after solidification.
Hyperbranched polyorganosiloxane fire retardant/epoxy resin/DDM system flame retardant resistance and thermotolerance test result are as following table.
The mensuration of limiting oxygen index(LOI): measure its flame retardant properties according to GB GB/T2406-93 (Plastics Combustion performance test methods: oxygen index method) and record its combustioncharacteristics on XYC-75 oxygen index measurer.
Vertical combustion performance measures: promulgate vertical combustion standard testing according to UnderwriterLaboratoryInc..Often organize at least 5 standard battens to test.
Table flame retardant resistance and thermotolerance test result
Claims (9)
1. a hyperbranched polyorganosiloxane, structural formula is as shown in (I):
2. the preparation method of a hyperbranched polyorganosiloxane according to claim 1:
A. the siloxanes of epoxy group(ing) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are put into and agitator are installed, reactor that temperature takes into account reflux condensing tube, stir 30 minutes at 25 ~ 60 DEG C;
B. then triphenylphosphine is added, stirring reaction 8 hours at 120 DEG C;
C. temperature is reduced to the siloxanes, the water that add methoxyl group in 60 DEG C of backward three-necked bottles, and ammoniacal liquor, stirring reaction 4.5 hours;
D. finally adding appropriate 1-chlorine trimethyl silane again reacts 1 hour, after end, products therefrom is placed in the beaker precipitated and separated that normal hexane is housed, collect lower floor's solution and remove unreacted material, lower floor's solution is carried out revolving steaming, until inclusion-free steams, finally obtain orange-yellow thick liquid product.
3., according to the preparation method of hyperbranched polyorganosiloxane according to claim 2, it is characterized in that, wherein, the molar ratio 1:1 ~ 1:1.5 of the siloxanes of epoxy group(ing) and the siloxanes of methoxyl group.
4., according to the preparation method of hyperbranched polyorganosiloxane according to claim 2, it is characterized in that, wherein, the ratio 1:0.5 ~ 1:1 of the siloxanes of epoxy group(ing) and the siloxanes of methoxyl group and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
5. according to the preparation method of the hyperbranched polyorganosiloxane one of claim 2-4 Suo Shu, it is characterized in that, wherein, the siloxanes of described epoxy group(ing) is γ-glycidyl ether oxygen propyl trimethoxy silicane.
6. according to the preparation method of the hyperbranched polyorganosiloxane one of claim 2-4 Suo Shu, it is characterized in that, wherein, the siloxanes of methoxyl group is dimethyldimethoxysil,ne.
7. comprise a composition for hyperbranched polyorganosiloxane according to claim 1, mainly consist of: with weight parts,
Epoxy resin 100 weight part,
Hyperbranched polyorganosiloxane 8.5-80 weight part,
4,4-diaminodiphenyl-methane 20 weight part.
8. according to the composition of hyperbranched polyorganosiloxane according to claim 7, it is characterized in that, wherein, epoxy resin is Racemic glycidol ethers, aromatic series or aliphatic epoxy resin.
9. according to the composition of the hyperbranched polyorganosiloxane described in claim 7 or 8, it is characterized in that, wherein, epoxy resin is novolac epoxy.
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| CN110628000A (en) * | 2019-09-11 | 2019-12-31 | 西北工业大学 | High-toughness flame-retardant medium-low temperature cured epoxy resin system and preparation method thereof |
| CN111234235A (en) * | 2020-02-24 | 2020-06-05 | 桂林理工大学 | Oligomeric silicon-oxygen phosphate flame retardant and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591288A (en) * | 2019-09-11 | 2019-12-20 | 西北工业大学 | Hyperbranched silicon-phosphorus synergistic flame retardant modified epoxy resin and preparation method thereof |
| CN110628000A (en) * | 2019-09-11 | 2019-12-31 | 西北工业大学 | High-toughness flame-retardant medium-low temperature cured epoxy resin system and preparation method thereof |
| CN110591288B (en) * | 2019-09-11 | 2022-04-15 | 西北工业大学 | Hyperbranched silicon-phosphorus synergistic flame retardant modified epoxy resin and preparation method thereof |
| CN111234235A (en) * | 2020-02-24 | 2020-06-05 | 桂林理工大学 | Oligomeric silicon-oxygen phosphate flame retardant and preparation method and application thereof |
| CN111234235B (en) * | 2020-02-24 | 2022-05-13 | 桂林理工大学 | Oligomeric silicon-oxygen phosphate flame retardant and preparation method and application thereof |
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