CN101016226A - Synthetic method and refining for dibromoneopentyl glycol - Google Patents
Synthetic method and refining for dibromoneopentyl glycol Download PDFInfo
- Publication number
- CN101016226A CN101016226A CN 200710019792 CN200710019792A CN101016226A CN 101016226 A CN101016226 A CN 101016226A CN 200710019792 CN200710019792 CN 200710019792 CN 200710019792 A CN200710019792 A CN 200710019792A CN 101016226 A CN101016226 A CN 101016226A
- Authority
- CN
- China
- Prior art keywords
- dibromoneopentyl glycol
- weight
- tetramethylolmethane
- synthetic method
- hour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 title claims description 51
- 238000010189 synthetic method Methods 0.000 title claims description 19
- 238000007670 refining Methods 0.000 title claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 60
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000002148 esters Chemical class 0.000 claims abstract description 26
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 40
- 239000012043 crude product Substances 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 23
- 150000007942 carboxylates Chemical class 0.000 claims description 19
- 230000032050 esterification Effects 0.000 claims description 16
- 238000005886 esterification reaction Methods 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 238000006467 substitution reaction Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims 2
- 238000010025 steaming Methods 0.000 claims 1
- SRGHNZAKTQALEA-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol dihydrobromide Chemical compound Br.Br.OCC(C)(C)CO SRGHNZAKTQALEA-UHFFFAOYSA-N 0.000 abstract 2
- 150000005690 diesters Chemical class 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 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 class 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 4
- 239000003063 flame retardant Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- -1 tribromoneoamyl alcohol Chemical compound 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesizing method of dibromide-neopentyl glycol, which comprises the following steps: esterifying pentaerythritol and acetic acid with density over 98%; dissolving and separating ester the acetic acid; aerating hydrogen bromide to substitute; insulating to separate diester of dibromide-neopentyl glycol; proceeding constant pressure decomposition through carbinol and inorganic acid under 0.4-0.6Mpa.
Description
Technical field
The present invention relates to a kind of synthetic method of dibromoneopentyl glycol, provide a kind of dibromoneopentyl glycol crude product that obtains that will synthesize to carry out the purified method simultaneously.
Background technology
Dibromoneopentyl glycol is a kind of novel brominated flame-retardant, and it both can be used as one of monomer of reaction, and preparation flame retardant type unsaturated polyester, urethane etc. also can directly add in High molecular weight polyethylene, the polystyrene foamed; As additive flame retardant, because its constitutional features, the product of making has outstanding flame retardant resistance, and the character of not fading under significant light stability and good anti-ultraviolet property, especially transparent flame-retarding product are exposed to the sun out of doors for a long time is that other fire retardants are incomparable.At present, the production technique of dibromoneopentyl glycol is to adopt tetramethylolmethane directly to follow the gas reaction of hydrogen bromide with reaction of liquid bromine hydracid or tetramethylolmethane, preceding a kind of temperature of reaction height, and dibromoneopentyl glycol content is about 67% in the crude product that the back becomes, product yield is low, energy consumption is high, and has tar to produce; Though a kind of temperature in back is low, because reactive activity is higher, is difficult to orienting response, general product is the mixture of dibromoneopentyl glycol, tribromoneoamyl alcohol, and dibromoneopentyl glycol content is generally 73% in the crude product, is difficult to separate, and yield is also lower.
Summary of the invention
The present invention is just in order to overcome above-mentioned deficiency, a kind of synthetic method of dibromoneopentyl glycol is provided, its reactive behavior height is easy to the location, temperature of reaction is low, the crude product dibromoneopentyl glycol content height that generates, the product yield height, main innovation is earlier tetramethylolmethane to be carried out two esterifications with concentration at the acetic acid more than 98%, occupy two groups, improve the ability and the purity of product orientation reaction, and then with the gas reaction of hydrogen bromide, carrying out ester again decomposes, specifically implement like this: the synthetic method of dibromoneopentyl glycol, tetramethylolmethane carries out esterification with concentration at the acetic acid more than 98% earlier, uses concentration at the isolated carboxylate of the acetate dissolution more than 98% again, feeds bromize hydrogen gas and carries out substitution reaction, isolate two carboxylates of dibromoneopentyl glycol after the insulation, carry out the constant voltage ester with methyl alcohol and mineral acid down in 0.4-0.6Mpa pressure then and decompose.
In this synthetic method, when tetramethylolmethane and acetic acid carried out esterification, the adding weight of acetic acid was 1.1-1.3 times of tetramethylolmethane weight, back flow reaction 4-6 hour.Adopt dehydration to steam sour mode after the esterification and isolate carboxylate, the time that acid is steamed in dehydration is controlled to be 2.5-3.5 hour, and temperature is 115-125 ℃.
During with the acetate dissolution carboxylate, the add-on of acetic acid is 0.7-1.1 a times of tetramethylolmethane weight, feed bromize hydrogen gas down at 85-105 ℃ and carry out substitution reaction, the feeding amount of hydrogen bromide is 1.1-1.25 a times of tetramethylolmethane weight, aeration time is 4-5 hour, and 90-100 ℃ of normal pressure insulation 3.5-5.5 hour.
Concentrate after insulation finishes and steam the acid separation, the still bottom product is two carboxylates of dibromoneopentyl glycol, when carrying out the ester decomposition with methyl alcohol and mineral acid, methanol usage is 1.5-1.8 a times of tetramethylolmethane weight, the consumption of mineral acid is the 3%-5% of tetramethylolmethane weight, the temperature that the constant voltage ester decomposes is 65-70 ℃, and the time that ester decomposes is 3.5-4.5 hour, and it is sulfuric acid or hydrochloric acid or Hydrogen bromide or other class acidoid that the constant voltage ester decomposes the mineral acid that can adopt.
Reaction equation is:
The product that ester decomposes decolours under 60-70 ℃ with gac, and the add-on of gac is the 1.5%-3.0% of tetramethylolmethane weight, and the time is 1.0-1.5 hour, after the filtration, filtrate concentrate the crude product dibromoneopentyl glycol.
The content of dibromoneopentyl glycol is greatly about about 88% in the crude product, in order to obtain high-quality dibromoneopentyl glycol, also need the crude product dibromoneopentyl glycol is made with extra care, operation is: dibromoneopentyl glycol refining, mixture dissolving dibromoneopentyl glycol crude product with the first alcohol and water, the weight ratio of methyl alcohol and water is 15-35: 85-65, the consumption of mixed solvent is 0.6-0.9 a times of dibromoneopentyl glycol crude product weight, 65-70 ℃ of insulation 1.0-1.5 hour, cool to 20-25 ℃ again, centrifugation goes out wet finished product, dry packing.The mother liquor of isolating behind the wet finished product can be handled through distillation, isolates mixed solvent and recycles, and pin is then treated under the still can reuse, and whole technology does not have waste residue and produces non-environmental-pollution.
Method of the present invention, temperature of reaction is low, and the crude product dibromoneopentyl glycol content of generation can reach about 88%, the product yield height, the purified tankage can be recycled, and no waste residue produces, and is a kind of method of more satisfactory production dibromoneopentyl glycol.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
Embodiment 1, and the synthetic method of dibromoneopentyl glycol is carried out esterification with concentration at the acetic acid more than 98% earlier with tetramethylolmethane, and the adding weight of acetic acid is 1.1 times of tetramethylolmethane weight, backflow esterification 5 hours; After the esterification, steam sour mode with dehydration and isolate carboxylate, it is 3.5 hours that the acid time is steamed in dehydration, and temperature is 115 ℃; Use concentration at the isolated carboxylate of the acetate dissolution more than 98% again, the add-on of acetic acid is 0.9 times of tetramethylolmethane weight, feed bromize hydrogen gas and under 85 ℃, carry out substitution reaction, the feeding amount of hydrogen bromide is 1.2 times of tetramethylolmethane weight, aeration time is 4 hours, then 95 ℃ of normal pressure insulations 3.5 hours; Isolate two carboxylates of dibromoneopentyl glycol after the insulation, carrying out the constant voltage ester with methyl alcohol and sulfuric acid under 0.6Mpa pressure decomposes, methanol usage is 1.7 times of tetramethylolmethane weight, the vitriolic consumption is 3% of a tetramethylolmethane weight, the temperature that the constant voltage ester decomposes is 70 ℃, and the time that ester decomposes is 4.5 hours; The product that ester decomposes decolours under 60 ℃ with gac, and the add-on of gac is 2% of a tetramethylolmethane weight, and the time is 1.0 hours, after the filtration, filtrate concentrate the crude product dibromoneopentyl glycol.
Embodiment 2, and the synthetic method of dibromoneopentyl glycol is carried out esterification with concentration at the acetic acid more than 98% earlier with tetramethylolmethane, and the adding weight of acetic acid is 1.2 times of tetramethylolmethane weight, backflow esterification 4 hours; After the esterification, steam sour mode with dehydration and isolate carboxylate, the time that acid is steamed in dehydration is controlled to be 2.5 hours, and temperature is 125 ℃; Use concentration at the isolated carboxylate of the acetate dissolution more than 98% again, the add-on of acetic acid is 1.1 times of tetramethylolmethane weight, feed bromize hydrogen gas and under 105 ℃, carry out substitution reaction, the feeding amount of hydrogen bromide is 1.1 times of tetramethylolmethane weight, aeration time is 4.5 hours, then 100 ℃ of normal pressure insulations 4.5 hours; Isolate two carboxylates of dibromoneopentyl glycol after the insulation, carrying out the constant voltage ester with methyl alcohol and hydrochloric acid under 0.5Mpa pressure decomposes, methanol usage is 1.8 times of tetramethylolmethane weight, the consumption of hydrochloric acid is 4% of a tetramethylolmethane weight, the temperature that the constant voltage ester decomposes is 65 ℃, and the time that ester decomposes is 4 hours; The product that ester decomposes decolours under 65 ℃ with gac, and the add-on of gac is 1.5% of a tetramethylolmethane weight, and the time is 1.5 hours, after the filtration, filtrate concentrate the crude product dibromoneopentyl glycol.
Embodiment 3, and the synthetic method of dibromoneopentyl glycol is carried out esterification with concentration at the acetic acid more than 98% earlier with tetramethylolmethane, and the adding weight of acetic acid is 1.3 times of tetramethylolmethane weight, backflow esterification 6 hours; After the esterification, steam sour mode with dehydration and isolate carboxylate, the time that acid is steamed in dehydration is controlled to be 3 hours, and temperature is 120 ℃; Use concentration at the isolated carboxylate of the acetate dissolution more than 98% again, the add-on of acetic acid is 0.7 times of tetramethylolmethane weight, feed bromize hydrogen gas and under 95 ℃, carry out substitution reaction, the feeding amount of hydrogen bromide is 1.25 times of tetramethylolmethane weight, aeration time is 5 hours, then 90 ℃ of normal pressure insulations 5.5 hours; Isolate two carboxylates of dibromoneopentyl glycol after the insulation, carrying out the constant voltage ester with methyl alcohol and Hydrogen bromide under 0.4Mpa pressure decomposes, methanol usage is 1.5 times of tetramethylolmethane weight, hydrobromic consumption is 5% of a tetramethylolmethane weight, the temperature that the constant voltage ester decomposes is 68 ℃, and the time that ester decomposes is 3.5 hours; The product that ester decomposes decolours under 70 ℃ with gac, and the add-on of gac is 3.0% of a tetramethylolmethane weight, and the time is 1.2 hours, after the filtration, filtrate concentrate the crude product dibromoneopentyl glycol.
Embodiment 4, the synthetic method of dibromoneopentyl glycol, after reference example 1 produces the crude product dibromoneopentyl glycol, make with extra care with the mixture dissolving dibromoneopentyl glycol crude product of first alcohol and water, the weight ratio of first alcohol and water is 30: 70 again, and the consumption of mixed solvent is 0.6 times of dibromoneopentyl glycol crude product weight, 70 ℃ of insulations 1.2 hours, cool to 25 ℃ again, centrifugation goes out wet finished product, dry packing; The mother liquor of isolating behind the wet finished product distills processing, isolates mixed solvent and recycles, the treated reuse of pin under the still.
Embodiment 5, the synthetic method of dibromoneopentyl glycol, after reference example 2 produces the crude product dibromoneopentyl glycol, make with extra care with the mixture dissolving dibromoneopentyl glycol crude product of first alcohol and water, the weight ratio of first alcohol and water is 15: 85 again, and the consumption of mixed solvent is 0.8 times of dibromoneopentyl glycol crude product weight, 65 ℃ of insulations 1.5 hours, cool to 23 ℃ again, centrifugation goes out wet finished product, dry packing; The mother liquor of isolating behind the wet finished product distills processing, isolates mixed solvent and recycles, the treated reuse of pin under the still.
Embodiment 6, the synthetic method of dibromoneopentyl glycol, after reference example 3 produces the crude product dibromoneopentyl glycol, make with extra care with the mixture dissolving dibromoneopentyl glycol crude product of first alcohol and water, the weight ratio of first alcohol and water is 35: 65 again, and the consumption of mixed solvent is 0.9 times of dibromoneopentyl glycol crude product weight, 68 ℃ of insulations 1 hour, cool to 20 ℃ again, centrifugation goes out wet finished product, dry packing; The mother liquor of isolating behind the wet finished product distills processing, isolates mixed solvent and recycles, the treated reuse of pin under the still.
Claims (10)
1. the synthetic method of dibromoneopentyl glycol, it is characterized in that tetramethylolmethane carries out esterification with concentration at the acetic acid more than 98% earlier, use concentration at the isolated carboxylate of the acetate dissolution more than 98% again, feed bromize hydrogen gas and carry out substitution reaction, isolate two carboxylates of dibromoneopentyl glycol after the insulation, carry out the constant voltage ester with methyl alcohol and mineral acid down in 0.4-0.6Mpa pressure then and decompose.
2. synthetic method according to claim 1 is characterized in that the mineral acid of constant voltage ester decomposition usefulness is sulfuric acid or hydrochloric acid or Hydrogen bromide.
3. synthetic method according to claim 1, when it is characterized in that tetramethylolmethane and acetic acid carry out esterification, the adding weight of acetic acid is 1.1-1.3 times of tetramethylolmethane weight, back flow reaction 4-6 hour.
4. synthetic method according to claim 1 is characterized in that adopting the sour mode of dehydration steaming to isolate carboxylate after the esterification, and the time that acid is steamed in dehydration is controlled to be 2.5-3.5 hour, and temperature is 115-125 ℃.
5. synthetic method according to claim 1, when it is characterized in that with the acetate dissolution carboxylate, the add-on of acetic acid is 0.7-1.1 a times of tetramethylolmethane weight, feed bromize hydrogen gas down at 85-105 ℃ and carry out substitution reaction, the feeding amount of hydrogen bromide is 1.1-1.25 a times of tetramethylolmethane weight, aeration time is 4-5 hour, then 90-100 ℃ of normal pressure insulation 3.5-5.5 hour.
6. synthetic method according to claim 1, two carboxylates that it is characterized in that dibromoneopentyl glycol carry out ester when decomposing, methanol usage is 1.5-1.8 a times of tetramethylolmethane weight, the consumption of mineral acid is the 3%-5% of tetramethylolmethane weight, the temperature that the constant voltage ester decomposes is 65-70 ℃, and the time that ester decomposes is 3.5-4.5 hour.
7. synthetic method according to claim 6, it is characterized in that the product that ester decomposes decolours under 60-70 ℃ with gac, the add-on of gac is the 1.5%-3.0% of tetramethylolmethane weight, and the time is 1.0-1.5 hour, after the filtration, filtrate concentrate the crude product dibromoneopentyl glycol.
8. refining by claim 1-7 synthetic dibromoneopentyl glycol, it is characterized in that mixture dissolving dibromoneopentyl glycol crude product with the first alcohol and water, the consumption of mixed solvent is 0.6-0.9 a times of dibromoneopentyl glycol crude product weight, 65-70 ℃ of insulation 1.0-1.5 hour, cool to 20-25 ℃ again, centrifugation goes out wet finished product, dry packing.
9. process for purification according to claim 8, the weight ratio that it is characterized in that the first alcohol and water is 15-35: 85-65.
10. process for purification according to claim 8, the mother liquor that it is characterized in that isolating behind the wet finished product distills processing, isolates mixed solvent and recycles, the treated reuse of pin under the still.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100197927A CN101016226B (en) | 2007-02-08 | 2007-02-08 | Synthetic method and refining for dibromoneopentyl glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100197927A CN101016226B (en) | 2007-02-08 | 2007-02-08 | Synthetic method and refining for dibromoneopentyl glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101016226A true CN101016226A (en) | 2007-08-15 |
| CN101016226B CN101016226B (en) | 2010-09-01 |
Family
ID=38725469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100197927A Expired - Fee Related CN101016226B (en) | 2007-02-08 | 2007-02-08 | Synthetic method and refining for dibromoneopentyl glycol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101016226B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031719A (en) * | 2012-12-28 | 2013-04-10 | 苏州市华智顾纺织有限公司 | Fabrication method of flame-retardant silk fabric |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932541A (en) * | 1971-08-12 | 1976-01-13 | The Dow Chemical Company | Process for the preparation of brominated pentaerythritols |
| DE3125338A1 (en) * | 1981-06-27 | 1983-01-13 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING BROMHYDRINES FROM POLYOLS |
| US4873377A (en) * | 1988-10-03 | 1989-10-10 | Ethyl Corporation | Preparation of dibromoneopentyl glycol |
-
2007
- 2007-02-08 CN CN2007100197927A patent/CN101016226B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031719A (en) * | 2012-12-28 | 2013-04-10 | 苏州市华智顾纺织有限公司 | Fabrication method of flame-retardant silk fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101016226B (en) | 2010-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101016227B (en) | Synthetic method and refining for tribromoneoamyl alcohol | |
| US8759575B2 (en) | Method for catalytically producing formic acid | |
| CN101492528B (en) | Method for synthesizing alicyclic epoxy resin by catalysis of solid-supported heteropoly acid catalyst | |
| CN104892623B (en) | A kind of preparation method of 5 Isosorbide Mononitrate | |
| BRPI0608734A2 (en) | process for the preparation of a composition useful as a fuel, and improvement in a process for preparation of a composition useful as a fuel | |
| CN102070575B (en) | New synthesis method of caronic anhydride | |
| CN102617432A (en) | Preparation method of tert-butylperoxy-2-ethylhexyl carbonate | |
| CN104761429A (en) | Dimethyl carbonate and ethylene glycol production process | |
| CN106588758A (en) | Synthetic process for 2-hydrazinylpyridine derivative | |
| CN101302158A (en) | A kind of waste polyester resource utilization method for synthesizing PVC plasticizer DOTP | |
| CN108997085A (en) | The recovery method and recovery system of by-product in a kind of dimethyl oxalate synthesis technology | |
| CN101016226B (en) | Synthetic method and refining for dibromoneopentyl glycol | |
| CN102174213B (en) | Rod-shaped crystal form melamine cyanurate fire retardant and preparation method thereof | |
| CN101376631B (en) | Environment-protective preparation method of diglycol ethylene dibenzoate plasticiser | |
| CN101265341A (en) | A kind of preparation method of epoxy plasticizer | |
| CN102219688A (en) | Method for improving thermal stability of dibutyl/diisobutyl phthalate | |
| CN106831421A (en) | The preparation method of di-tert-butyl dicarbonate | |
| CN114213430A (en) | Preparation method of 4-aminothiophene [3,2-d ] pyrimidine-7-carboxylic acid and protein kinase inhibitor intermediate | |
| CN110156581B (en) | A method for one-step photocatalytic lignin depolymerization and amination synthesis of nitrogen-containing aromatic compounds | |
| CN106496487A (en) | Bio-based flame-retardant polyol and preparation method and application thereof | |
| CN107312052A (en) | A kind of preparation method of Methyllprednisolone | |
| CN113385225A (en) | Supermolecule ionic liquid catalyst and preparation method and application thereof | |
| CN103288645B (en) | Separation of dimethyl ether in the technique of alcoholysis of urea co-producing dimethyl carbonate and dme also reclaims the method for ammonia | |
| CN104262395A (en) | High-pressure oxidation synthesis process and device of tris (hydroxymethyl) phosphine oxide (THPO) | |
| CN105906550A (en) | Preparation method of UV770 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100901 Termination date: 20200208 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |