CN104710619B - Fire-retardant carbon forming agent poly dimethyl silicic acid is to benzene diester polymer and preparation method thereof - Google Patents
Fire-retardant carbon forming agent poly dimethyl silicic acid is to benzene diester polymer and preparation method thereof Download PDFInfo
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- CN104710619B CN104710619B CN201510102435.1A CN201510102435A CN104710619B CN 104710619 B CN104710619 B CN 104710619B CN 201510102435 A CN201510102435 A CN 201510102435A CN 104710619 B CN104710619 B CN 104710619B
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- silicic acid
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- hydroquinone
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- benzene
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- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 118
- -1 benzene diester Chemical class 0.000 title claims abstract description 57
- ONCIQCKBUSMDIK-UHFFFAOYSA-N dihydroxy(dimethoxy)silane Chemical compound CO[Si](O)(O)OC ONCIQCKBUSMDIK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000003063 flame retardant Substances 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000642 polymer Polymers 0.000 title claims abstract description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- 238000009413 insulation Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- 230000006837 decompression Effects 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005194 fractionation Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- HBWBYLWXCYPWAV-UHFFFAOYSA-N [N].OC1=CC=CC=C1O Chemical compound [N].OC1=CC=CC=C1O HBWBYLWXCYPWAV-UHFFFAOYSA-N 0.000 claims 2
- 238000000967 suction filtration Methods 0.000 claims 2
- 239000005046 Chlorosilane Substances 0.000 claims 1
- 230000001133 acceleration Effects 0.000 claims 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 32
- 239000000463 material Substances 0.000 abstract description 16
- 239000003610 charcoal Substances 0.000 abstract description 8
- 239000004952 Polyamide Substances 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920002647 polyamide Polymers 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 229910000077 silane Inorganic materials 0.000 abstract 2
- SSQNAPWMQSPZRM-UHFFFAOYSA-N benzene-1,4-diol;sodium Chemical compound [Na].OC1=CC=C(O)C=C1 SSQNAPWMQSPZRM-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 29
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000006073 displacement reaction Methods 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 229920001707 polybutylene terephthalate Polymers 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-DYCDLGHISA-N Deuterium chloride Chemical compound [2H]Cl VEXZGXHMUGYJMC-DYCDLGHISA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Abstract
The present invention relates to a kind of fire-retardant carbon forming agent poly dimethyl silicic acid to benzene diester polymer and preparation method thereof, and the structure of the polymer is shown below：
Description
Technical field
The present invention relates to a kind of fire-retardant carbon forming agent poly dimethyl silicic acid of silicon systems to benzene diester polymer and preparation method thereof, should
Polymer is suitable as the fire-retardant carbon forming agent of polyolefin, polyester, polyamide, epoxy resin, unsaturated-resin etc..
Background technology
Solve the problems, such as the inflammable of synthesis high molecular material, most efficient method is that fire retardant is added in the material, but fire-retardant
Agent generally can prevent to slow down the burning of material or material is made to become increasingly difficult to fire, and cannot change the spy of melt phase change when material is heated
Property, i.e., it can become liquid flowing or drippage when material burns at high temperature, mobile with flame can cause second-time burning.For
Inflammable, the drippage problem of synthetic material are solved, most efficient method is to add carbon forming agent while fire retardant is added or add
Enter again to have with fire retardation the auxiliary agent of char forming ability, i.e., fire-retardant carbon forming agent.The people such as pentaerythrite are it has been found that certain
It acts at charcoal, is also applied in certain materials, but most carbon forming agent there are polarity big, hygroscopic, decomposition temperature at present
The deficiencies of low and poor processability.Element silicon is an element for being not easy volatilization gasification, it is of the same clan, electronic structure with carbon
Similar, silicon, carbon structure dehydration carbonization are easy to generate fine and close silicon layer of charcoal under high temperature, and can play fire retardation can overcome synthesis again
The melting drippage problem of material.Therefore there is critically important realistic meaning to the research of organosilicon or siliceous fire-retardant carbon forming agent.
It is poly- the invention discloses the fire-retardant carbon forming agent of silicon systems is prepared using two halosilanes of dimethyl and hydroquinone as primary raw material
Dimethyl silicic acid is to benzene diester polymer.Element silicon can promote high molecular material at charcoal, fine and close silicon layer of charcoal be generated, by combustibles
Keep apart with oxygen, and can effectively prevent melt polymer material and drip to form second-time burning.Basic material of the present invention is inexpensively easy
, have a wide range of application, there is good application and development foreground.
Invention content
It is an object of the present invention to proposing a kind of fire-retardant carbon forming agent poly dimethyl silicic acid of silicon systems to benzene diester polymer,
Its is fire-retardant good at charcoal, can overcome deficiency in the prior art.
For achieving the above object, present invention employs following technical solutions：
Poly dimethyl silicic acid is to benzene diester polymer, which is characterized in that the structure of the polymer is shown below：
N=20~50 in formula.
Another object of the present invention is to propose preparation method of the poly dimethyl silicic acid to benzene diester polymer, technique letter
Single, equipment investment is few, is easy to large-scale production, and raw material is cheap and easy to get, health at low cost, and this method one is：
Equipped with blender, thermometer and condenser pipe, and in the condenser pipe reactor suitable for reading equipped with drying tube, use nitrogen
The air in reactor is displaced, hydroquinone is dissolved in suitable organic solvent, is added relative to 2~2.5 times of hydroquinone
Mole triethylamine, be added dropwise with equimolar two halosilanes of dimethyl of hydroquinone, it is not high with rate of addition controlling reaction temperature
In 40 DEG C, 7~14h is reacted after dripping off at 40 DEG C~70 DEG C；First of the quality grams relative to product theory quality 1% is added dropwise again
Alcohol makees end-capping reagent, insulation reaction 0.5h；It is cooled to 30 DEG C to wash twice hereinafter, adding appropriate volume distilled water, liquid separation, by institute
Obtained organic layer is dried with drier, is filtered, and filtrate decompression is distilled off organic solvent, obtains poly dimethyl silicic acid to benzene
Diester.
This method two is：
In the reactor equipped with blender, thermometer and division box, the air in reactor is displaced with nitrogen, is added
Enter hydroquinone, organic solvent and the sodium hydroxide relative to 2 times moles of hydroquinone, heating reflux reaction 3h quantitatively to separate
The water of generation；30 DEG C are cooled to hereinafter, dropwise addition and equimolar two halosilanes of dimethyl of hydroquinone, anti-with rate of addition control
It answers temperature to be not higher than 50 DEG C, 80 DEG C~120 DEG C is warming up to after dripping off, 6~10h of insulation reaction；60 DEG C are cooled to, then quality is added dropwise
Grams makees end-capping reagent, insulation reaction 0.5h relative to the methanol of product theory quality 1%；30 DEG C are cooled to remove hereinafter, filtering
Solvent and a small amount of low boilers are distilled off in sodium halide and a small amount of insoluble solids, filtrate decompression, obtain poly dimethyl silicic acid to benzene two
Ester.
This method three is：
In the reactor equipped with blender, thermometer and fractionating device, the air in reactor is displaced with nitrogen, is added
Enter hydroquinone, organic solvent and the sodium methoxide relative to 2 times moles of hydroquinone, heating fractionation reaction 2h controls still
It pushes up temperature and is not higher than 65 DEG C, quantitatively separate the methanol of generation；30 DEG C are cooled to hereinafter, being added dropwise and the equimolar diformazan of hydroquinone
Two halosilanes of base are not higher than 50 DEG C with rate of addition controlling reaction temperature, 80 DEG C~120 DEG C are warming up to after dripping off, insulation reaction 6
~10h；60 DEG C are cooled to, then quality grams is added dropwise and makees end-capping reagent, insulation reaction relative to the methanol of product theory quality 1%
0.5h；It is cooled to 30 DEG C and removes sodium halide and a small amount of insoluble solids hereinafter, filtering, solvent and a small amount of low is distilled off in filtrate decompression
Boiling point object obtains poly dimethyl silicic acid to benzene diester.
Organic solvent described in method one as above is toluene, dimethylbenzene, chloroform or dichloroethanes, dosage volume ml
It is 10~20 times of hydroquinone quality grams.
Addition appropriate volume distilled water described in method one as above is that the volume ml of distilled water is product theory quality
2~6 times of grams.
Drier described in method one as above is anhydrous sodium sulfate or anhydrous magnesium sulfate, and dosage quality grams is organic molten
The 5%~10% of agent volume ml.
Organic solvent described in method two and method three as above is benzene, toluene or dimethylbenzene, and dosage volume ml is
10~20 times of hydroquinone quality grams.
Two halosilanes of dimethyl described in method one, method two and method three as above are dimethyldichlorosilane or dimethyl
Two bromo-silicanes.
The poly dimethyl silicic acid of the present invention is pale red solid powder to benzene diester, and yield is 90.4%~96.7%, point
It is 358 DEG C ± 5 DEG C to solve temperature.It is suitable as the resistance of the materials such as polyolefin, polyester, polyamide, epoxy resin, unsaturated-resin
Fire carbon forming agent.The poly dimethyl silicic acid is shown below to the preparation process principle of benzene diester：
Or
RONa is NaOH or CH in formula3ONa, X=Cl or Br, n=20~50.
Compared with prior art, the beneficial effects of the present invention are：
1. poly dimethyl silicic acid of the present invention has into charcoal effect to benzene diester silicon containing ignition-proof element, can effectively prevent material
Melted by heating is dripped and the second-time burning of generation, and does not contain halogen, belongs to environmentally friendly fire-retardant carbon forming agent.
2. poly dimethyl silicic acid of the present invention has C-Si keys, is to connecting on silicon atom in two ester structure of benzene there are two methyl
Organosilicon structures, organosilicon structures stability is good, water resistance is strong, and when burning is more easily generated fine and close charcoal-silicon layer, flame retardant effect
It is better.
3. poly dimethyl silicic acid of the present invention had not only made catalyst to triethylamine used in benzene diester preparation process but also had made acid binding agent,
And the triethylamine halide salt generated is easily separated.
4. poly dimethyl silicic acid of the present invention in benzene diester preparation process with methanol to being blocked, it is active both to have removed chemical property
End group Si-Cl, acidification can be played again by reacting the hydrogen halides that quantitatively generates, and end group sodium phenolate is quantitatively become phenol hydroxyl
Base enormously simplifies post-processing flow, has novelty, there is good energy economy ＆ environment benefit.
5. poly dimethyl silicic acid of the present invention is simpler to the phenol sodium method preparation process of benzene diester, it is easier to the purification of product point
From.
6. poly dimethyl silicic acid of the present invention is big to benzene diester molecular weight, volatility is low, symmetry is good, physical and chemical performance is steady
Fixed, decomposition temperature is high, and the phenyl ring contained has the polytropism of electronic structure, good with high molecular material compatibility, is conducive to change
The mechanical property of kind material, adapts to the high temperature process of engineering material.
Description of the drawings
Following attached drawing is provided in order to further illustrate the structure and performance spy of product.
1, poly dimethyl silicic acid refers to Figure of description Fig. 1 to the infrared spectrogram of benzene diester；
Fig. 1 shows 3423.6cm-1For the stretching vibration absworption peak of O-H on sealing end hydroquinone, 2967.2cm-1For methyl
C-H stretching vibration absworption peak, 3091.1cm-1For the stretching vibration absworption peak of C-H on phenyl ring, 1507.3cm-1For phenyl ring
Characteristic absorption peak, 1258.3cm-1For the stretching vibration absworption peak of C-O, 1000.7cm-1For the characteristic absorption peak of Si-O-C,
809.2cm-1For the characteristic absorption peak of Si-C.
2, poly dimethyl silicic acid refers to Figure of description Fig. 2 to the nuclear magnetic spectrogram of benzene diester；
Fig. 2 shows that deuterochloroform makees solvent, and δ 6.64-6.86 are hydrogen peak on phenyl ring, and δ 0.26-0.37 are SiCH3Upper methyl
Hydrogen peak, δ 7.26 are the proton peak that solvent carbon deuterium chloride exchanges.
3,2 product poly dimethyl silicic acid of embodiment refers to Figure of description Fig. 3 to the GPC molecular weight spectrograms of benzene diester；
Fig. 3 shows that poly dimethyl silicic acid is 7.38 × 10 to benzene diester weight average molecular weight3, number-average molecular weight be 3.61 ×
103, profile exponent 2.044.
Specific embodiment
Technical scheme of the present invention is described further below in conjunction with specific implementation mode.
Embodiment 1 is equipped with blender, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouth bottle, with the air in nitrogen displacement bottle falling, 5.50g (0.05mol) hydroquinone, 80ml dichloroethanes and 10.1g is added
(0.1mol) triethylamine is added dropwise 6.45g (0.05mol) dimethyldichlorosilane, is not higher than with rate of addition controlling reaction temperature
40 DEG C, 65 DEG C are warming up to after dripping off, insulation reaction 9h；0.08g methanol is added dropwise again and makees end-capping reagent, insulation reaction 0.5h；It is cooled to
30 DEG C wash twice hereinafter, being separately added into 30ml distilled water again, liquid separation, and gained dichloroethanes layer is carried out with 4g anhydrous sodium sulfates
It is dry, it filters, filtrate decompression is distilled off dichloroethanes, obtains poly dimethyl silicic acid to benzene diester, yield：92.7%.
Embodiment 2 is equipped with blender, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouth bottle, with the air in nitrogen displacement bottle falling, 5.50g (0.05mol) hydroquinone, 110ml toluene and 12.63g is added
6.45g (0.05mol) dimethyldichlorosilane is added dropwise in (0.125mol) triethylamine, not high with rate of addition controlling reaction temperature
In 40 DEG C, 70 DEG C are warming up to after dripping off, insulation reaction 7h；0.08g methanol is added dropwise again and makees end-capping reagent, insulation reaction 0.5h；Cooling
It is washed twice to 30 DEG C hereinafter, being separately added into 30ml distilled water again, liquid separation, gained toluene layer is done with 6g anhydrous magnesium sulfates
It is dry, it filters, filtrate decompression is distilled off toluene, obtains poly dimethyl silicic acid to benzene diester, yield：93.5%, weight average molecular weight：
7.38×103, number-average molecular weight：3.61×103, profile exponent：2.044.
Embodiment 3 is equipped with blender, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouth bottle, with the air in nitrogen displacement bottle falling, 5.50g (0.05mol) hydroquinone, 80ml dimethylbenzene and 11.11g is added
(0.11mol) triethylamine is added dropwise 6.45g (0.05mol) dimethyldichlorosilane, is not higher than with rate of addition controlling reaction temperature
40 DEG C, 50 DEG C are warming up to after dripping off, insulation reaction 12h；0.08g methanol is added dropwise again and makees end-capping reagent, insulation reaction 0.5h；It is cooled to
30 DEG C wash twice hereinafter, being separately added into 50ml distilled water again, liquid separation, and gained diformazan benzene layer is done with 8g anhydrous sodium sulfates
It is dry, it filters, filtrate decompression is distilled off dimethylbenzene, obtains poly dimethyl silicic acid to benzene diester, yield：91.6%.
Embodiment 4 is equipped with blender, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouth bottle, with the air in nitrogen displacement bottle falling, 5.50g (0.05mol) hydroquinone, 90ml chloroforms and 12.63g is added
6.45g (0.05mol) dimethyldichlorosilane is added dropwise in (0.125mol) triethylamine, not high with rate of addition controlling reaction temperature
In 40 DEG C, after dripping off at 40 DEG C, insulation reaction 14h；0.08g methanol is added dropwise again and makees end-capping reagent, insulation reaction 0.5h；It is cooled to
30 DEG C wash twice hereinafter, being separately added into 30ml distilled water again, liquid separation, and gained chloroform layer is done with 5g anhydrous magnesium sulfates
It is dry, it filters, filtrate decompression is distilled off chloroform, obtains poly dimethyl silicic acid to benzene diester, yield：90.4%.
Embodiment 5 is equipped with blender, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouth bottle, with the air in nitrogen displacement bottle falling, 5.50g (0.05mol) hydroquinone, 110ml toluene and 10.1g is added
(0.1mol) triethylamine is added dropwise two bromo-silicane of 10.9g (0.05mol) dimethyl, is not higher than with rate of addition controlling reaction temperature
40 DEG C, 60 DEG C are warming up to after dripping off, insulation reaction 10h；0.08g methanol is added dropwise again and makees end-capping reagent, insulation reaction 0.5h；It is cooled to
30 DEG C wash twice hereinafter, being separately added into 20ml distilled water again, liquid separation, and gained toluene layer is done with 10g anhydrous sodium sulfates
It is dry, it filters, filtrate decompression is distilled off toluene, obtains poly dimethyl silicic acid to benzene diester, yield：92.2%, weight average molecular weight：
7.9×103, number-average molecular weight：3.7×103, profile exponent：2.135.
Embodiment 6 is equipped with blender, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouth bottle, with the air in nitrogen displacement bottle falling, 5.50g (0.05mol) hydroquinone, 100ml chloroforms and 11.11g is added
(0.11mol) triethylamine is added dropwise two bromo-silicane of 10.9g (0.05mol) dimethyl, is not higher than with rate of addition controlling reaction temperature
40 DEG C, after dripping off at 40 DEG C, insulation reaction 14h；0.08g methanol is added dropwise again and makees end-capping reagent, insulation reaction 0.5h；It is cooled to 30
It DEG C being washed twice hereinafter, being separately added into 40ml distilled water again, gained chloroform layer is dried with 6g anhydrous sodium sulfates for liquid separation,
It filters, filtrate decompression is distilled off chloroform, obtains poly dimethyl silicic acid to benzene diester, yield：91.3%.
Embodiment 7 is equipped with blender, thermometer and condenser pipe, and in the condenser pipe 250ml tetra- suitable for reading equipped with drying tube
In mouth bottle, with the air in nitrogen displacement bottle falling, 5.50g (0.05mol) hydroquinone, 80ml dimethylbenzene and 12.63g is added
Two bromo-silicane of 10.9g (0.05mol) dimethyl is added dropwise in (0.125mol) triethylamine, not high with rate of addition controlling reaction temperature
In 40 DEG C, 70 DEG C are warming up to after dripping off, insulation reaction 7h；0.08g methanol is added dropwise again and makees end-capping reagent, insulation reaction 0.5h；Cooling
It is washed twice to 30 DEG C hereinafter, being separately added into 40ml distilled water again, liquid separation, gained diformazan benzene layer is carried out with 8g anhydrous magnesium sulfates
It is dry, it filters, filtrate decompression is distilled off dimethylbenzene, obtains poly dimethyl silicic acid to benzene diester, yield：94.7%.
Embodiment 8 is in the 250ml four-hole bottles equipped with blender, thermometer and division box, in nitrogen displacement bottle falling
Air, be added 5.50g (0.05mol) hydroquinone, 110ml benzene and 4g (0.1mol) sodium hydroxide, heating reflux reaction 3h,
Quantitatively separate the water of generation；30 DEG C are cooled to, 6.45g (0.05mol) dimethyldichlorosilane is added dropwise, it is anti-with rate of addition control
Should degree of forcing be not higher than 50 DEG C, 80 DEG C are warming up to after dripping off, insulation reaction 10h；60 DEG C are cooled to, then 0.08g methanol is added dropwise and seals
Hold agent, insulation reaction 0.5h；It is cooled to 30 DEG C and removes sodium chloride and a small amount of insoluble solids hereinafter, filtering, filtrate decompression distillation removes
Solvent and a small amount of low boilers are gone, obtain poly dimethyl silicic acid to benzene diester, yield：93.9%.
Embodiment 9 is in the 250ml four-hole bottles equipped with blender, thermometer and fractionating device, in nitrogen displacement bottle falling
Air, 5.50g (0.05mol) hydroquinone, 90ml toluene and 5.4g (0.1mol) sodium methoxide, heating fractionation reaction is added
2h, control fractionation column top temperature are not higher than 65 DEG C, quantitatively separate the methanol of generation；30 DEG C are cooled to, 6.45g is added dropwise
(0.05mol) dimethyldichlorosilane is not higher than 50 DEG C with rate of addition controlling reaction temperature, 110 DEG C is warming up to after dripping off, protects
Temperature reaction 8h；60 DEG C are cooled to, then 0.08g methanol is added dropwise and makees end-capping reagent, insulation reaction 0.5h；30 DEG C are cooled to hereinafter, filtering
It removes sodium chloride and a small amount of insoluble solids, filtrate decompression is distilled off solvent and a small amount of low boilers, obtains poly dimethyl silicic acid pair
Benzene diester, yield：94.5%, weight average molecular weight：8.0×103, number-average molecular weight：4.1×103, profile exponent：1.951.
Embodiment 10 is in the 250ml four-hole bottles equipped with blender, thermometer and division box, in nitrogen displacement bottle falling
Air, 5.50g (0.05mol) hydroquinone, 80ml dimethylbenzene and 4g (0.1mol) sodium hydroxide, heating reflux reaction is added
3h quantitatively separates the water of generation；30 DEG C are cooled to, two bromo-silicane of 10.9g (0.05mol) dimethyl is added dropwise, with rate of addition control
Reaction temperature processed is not higher than 50 DEG C, 120 DEG C is warming up to after dripping off, insulation reaction 6h；60 DEG C are cooled to, then 0.08g methanol is added dropwise
Make end-capping reagent, insulation reaction 0.5h；It is cooled to 30 DEG C and removes sodium bromide and a small amount of insoluble solids hereinafter, filtering, filtrate decompression is steamed
Solvent and a small amount of low boilers are gone in distillation, obtain poly dimethyl silicic acid to benzene diester, yield：96.7%, weight average molecular weight：8.48×
103, number-average molecular weight：4.32×103, profile exponent：1.963.
Embodiment 11 is in the 250ml four-hole bottles equipped with blender, thermometer and fractionating device, in nitrogen displacement bottle falling
Air, 5.50g (0.05mol) hydroquinone, 60ml toluene and 5.4g (0.1mol) sodium methoxide, heating fractionation reaction is added
2h, control fractionation column top temperature are not higher than 65 DEG C, quantitatively separate the methanol of generation；30 DEG C are cooled to, 10.9g is added dropwise
Two bromo-silicane of (0.05mol) dimethyl is not higher than 50 DEG C with rate of addition controlling reaction temperature, 110 DEG C is warming up to after dripping off, protects
Temperature reaction 8h；60 DEG C are cooled to, then 0.08g methanol is added dropwise and makees end-capping reagent, insulation reaction 0.5h；30 DEG C are cooled to hereinafter, filtering
It removes sodium bromide and a small amount of insoluble solids, filtrate decompression is distilled off solvent and a small amount of low boilers, obtains poly dimethyl silicic acid pair
Benzene diester, yield：95.5%.
Embodiment 12 is in the 250ml four-hole bottles equipped with blender, thermometer and fractionating device, in nitrogen displacement bottle falling
Air, 5.50g (0.05mol) hydroquinone, 100ml dimethylbenzene and 5.4g (0.1mol) sodium methoxide is added, heating fractionation is anti-
2h, control fractionation column top temperature is answered to be not higher than 65 DEG C, quantitatively separate the methanol of generation；30 DEG C are cooled to, 6.45g is added dropwise
(0.05mol) dimethyldichlorosilane is not higher than 50 DEG C with rate of addition controlling reaction temperature, 110 DEG C is warming up to after dripping off, protects
Temperature reaction 8h；60 DEG C are cooled to, then 0.08g methanol is added dropwise and makees end-capping reagent, insulation reaction 0.5h；30 DEG C are cooled to hereinafter, filtering
It removes sodium chloride and a small amount of insoluble solids, filtrate decompression is distilled off solvent and a small amount of low boilers, obtains poly dimethyl silicic acid pair
Benzene diester, yield：95.8%.
The poly dimethyl silicic acid of above-mentioned preparation is applied to polybutylene terephthalate (PBT) by inventor to benzene diester
In (PBT).Poly dimethyl silicic acid is taken in varing proportions after mixing, to be squeezed out with extruder to benzene diester and PBT, diameter is made
For the batten of 3mm, and its carbon-forming performance is tested, listing part test, the results are shown in Table 1：
Carbon-forming performance data of the 1 poly dimethyl silicic acid of table to benzene diester
As can be seen that it can be completely when poly dimethyl silicic acid adds 10%~15% to benzene diester in PBT according to table 1
The defect of drippage is easily melted when PBT being overcome to burn.Therefore, poly dimethyl silicic acid of the present invention has well into charcoal benzene diester
Energy.
The poly dimethyl silicic acid of above-mentioned preparation is also carried out compounding to benzene diester and ammonium polyphosphate (APP) and answered by inventor
For (PP) in polypropylene.Reference：GB/T2406-2008《Plastics Combustion method for testing performance-oxygen index method》The pole of sample
Limited oxygen index.Take poly dimethyl silicic acid that benzene diester, APP and PP in varing proportions after mixing, are squeezed out with extruder, are made
The batten of a diameter of 3mm, and its flame retardant property is tested, listing part test, the results are shown in Table 2：
Flame retardant property data of the 2 poly dimethyl silicic acid of table to benzene diester
According to table 2 as can be seen that poly dimethyl silicic acid shows significantly benzene diester and APP compoundings in fire-retardant PP
Fire-retardant synergetic.
Claims (3)
1. a kind of fire-retardant carbon forming agent poly dimethyl silicic acid is to the preparation method of benzene diester, which is characterized in that this method is：
In the reactor equipped with blender, thermometer and division box, the air in reactor, addition pair are displaced with nitrogen
Benzenediol, organic solvent and the sodium hydroxide relative to 2 times moles of hydroquinone, heating reflux reaction 3h quantitatively separate generation
Water；Be cooled to 30 DEG C hereinafter, be added dropwise with two bromo-silicane of the equimolar dimethyldichlorosilane of hydroquinone or dimethyl, with drop
Acceleration Control reaction temperature is not higher than 50 DEG C, 80 DEG C~120 DEG C is warming up to after dripping off, 6~10h of insulation reaction；It is cooled to 60
DEG C, then quality grams is added dropwise and makees end-capping reagent, insulation reaction 0.5h relative to the methanol of product theory quality 1%；It is cooled to 30 DEG C
Hereinafter, suction filtration removes sodium halide and a small amount of insoluble solids, filtrate decompression are distilled off solvent and a small amount of low boilers, obtain poly- diformazan
Base silicic acid is shown below to benzene diester, the structure of the polymer：
N is more than 20 and is less than or equal to 50 in formula.
2. a kind of fire-retardant carbon forming agent poly dimethyl silicic acid is to the preparation method of benzene diester, which is characterized in that this method is：
In the reactor equipped with blender, thermometer and fractionating device, the air in reactor, addition pair are displaced with nitrogen
Benzenediol, organic solvent and the sodium methoxide relative to 2 times moles of hydroquinone, heating fractionation reaction 2h, control fractionation capital temperature
Degree is not higher than 65 DEG C, quantitatively separates the methanol of generation；30 DEG C are cooled to hereinafter, being added dropwise and the equimolar dimethyl of hydroquinone two
Two bromo-silicane of chlorosilane or dimethyl is not higher than 50 DEG C with rate of addition controlling reaction temperature, 80 DEG C~120 is warming up to after dripping off
DEG C, 6~10h of insulation reaction；60 DEG C are cooled to, then quality grams is added dropwise and is blocked relative to the methanol of product theory quality 1%
Agent, insulation reaction 0.5h；30 DEG C are cooled to hereinafter, suction filtration removes sodium halide and a small amount of insoluble solids, filtrate decompression are distilled off
Solvent and a small amount of low boilers obtain poly dimethyl silicic acid to benzene diester, and the structure of the polymer is shown below：
N is more than 20 and is less than or equal to 50 in formula.
3. poly dimethyl silicic acid according to claim 1 or claim 2 is to the preparation method of benzene diester, which is characterized in that described has
Solvent is benzene or dimethylbenzene, and dosage volume ml is 10~20 times of hydroquinone quality grams.
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