CN112209964A - Preparation method of TCPP (trichloropropylphosphate) flame retardant - Google Patents
Preparation method of TCPP (trichloropropylphosphate) flame retardant Download PDFInfo
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- CN112209964A CN112209964A CN202011125568.8A CN202011125568A CN112209964A CN 112209964 A CN112209964 A CN 112209964A CN 202011125568 A CN202011125568 A CN 202011125568A CN 112209964 A CN112209964 A CN 112209964A
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- molecular distillation
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 24
- 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 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- LOOCNDFTHKSTFY-UHFFFAOYSA-N 1,1,2-trichloropropyl dihydrogen phosphate Chemical compound CC(Cl)C(Cl)(Cl)OP(O)(O)=O LOOCNDFTHKSTFY-UHFFFAOYSA-N 0.000 title abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 15
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012043 crude product Substances 0.000 claims abstract description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 4
- 238000000199 molecular distillation Methods 0.000 claims description 38
- 239000010409 thin film Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims 4
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000010408 film Substances 0.000 claims 1
- -1 aldehyde compound Chemical class 0.000 abstract description 26
- 239000002253 acid Substances 0.000 abstract description 22
- 239000002351 wastewater Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 23
- 238000009835 boiling Methods 0.000 description 22
- 238000001514 detection method Methods 0.000 description 18
- 238000005070 sampling Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 239000003513 alkali Substances 0.000 description 10
- 230000003068 static effect Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000004821 distillation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- XKCQNWLQCXDVOP-UHFFFAOYSA-N tris(2-chloropropan-2-yl) phosphate Chemical compound CC(C)(Cl)OP(=O)(OC(C)(C)Cl)OC(C)(C)Cl XKCQNWLQCXDVOP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a TCPP (trichloropropylphosphate) flame retardant, which comprises the step of reacting phosphorus oxychloride with propylene oxide under the action of a Lewis acid catalyst to obtain a TCPP crude product. On the premise of not influencing the product yield and the acid value, compared with the traditional process, the method does not generate waste water, can better reduce the environmental protection pressure and bring greater economic benefits, and the TCPP finished product prepared by the method has the aldehyde compound content of less than 10ppm and small smell; the invention can also be used for preparing the phosphate flame retardant by reacting other epoxy compounds with phosphorus oxychloride.
Description
Technical Field
The invention belongs to the technical field of preparation of phosphate flame retardants, and particularly relates to a preparation method of a TCPP flame retardant.
Background
Tris (chloroisopropyl) phosphate (TCPP for short) is mainly used for the production of flame retardant and additive flame retardant for soft and hard polyurethane foam, epoxy resin, propylene resin, polystyrene, cellulose acetate, ethyl cellulose, phenolic resin, polyvinyl acetate, polyvinyl chloride, rubber and paint. It is especially suitable for the production of compound polyurethane foam, unsaturated resin and phenolic plastics.
In the prior art, the TCPP flame retardant is prepared by reacting phosphorus oxychloride with propylene oxide under the action of a Lewis acid catalyst to obtain a TCPP crude product, carrying out alkali washing and liquid separation on the crude product, washing a material layer to be neutral, carrying out liquid separation and dehydration to obtain a finished TCPP product. The method generates a large amount of wastewater in the processes of alkali washing and water washing, a certain environmental protection pressure is generated in the later period, a large amount of capital and manpower are needed for processing, and the content of the finished product aldehyde compound of TCPP obtained by the method is high and often exceeds 100ppm, so that the product smell is large.
Patent 200910264987.7 discloses that TCPP is obtained by first reacting a crude TCPP product, then treating the crude TCPP product, adding an oxidant solution to react with an aldehyde compound to generate an acid substance which is non-toxic, harmless, reactive with an alkali and soluble in water, and then removing the acid by alkali washing and water washing to obtain TCPP containing substantially no aldehyde. Although TCPP with lower aldehyde substances is synthesized by the method on the premise of not influencing yield and acid value, the defect of large odor of the product is overcome, alkaline washing is carried out in the preparation process, and waste water generated by water washing needs subsequent environmental protection treatment, so that certain environmental protection pressure and cost expenditure are caused. The above process still has shortcomings that are worth improving.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a TCPP flame retardant, which does not influence the product yield and the acid value and has lower content of the obtained finished product aldehyde compound.
The preparation method of the TCPP flame retardant comprises the steps of reacting phosphorus oxychloride with propylene oxide under the catalytic action of a Lewis acid catalyst to obtain a TCPP crude product, and is characterized in that the prepared crude product is evaporated and removed by a thin film evaporator under the vacuum condition, and then secondary removal is carried out on the rest low-boiling-point substances under the high vacuum condition by primary molecular distillation; finally, the material is distilled out under the condition of high vacuum through secondary molecular distillation, and the finished product of TCPP is obtained.
The preparation method of the TCPP flame retardant is characterized in that the vacuum requirement of a thin film evaporator is 80-200Pa, and preferably 80-120 Pa.
The preparation method of the TCPP flame retardant is characterized in that the temperature of the thin film evaporator is 90-130 ℃, and preferably 100-120 ℃.
The preparation method of the TCPP flame retardant is characterized in that the feeding speed of the thin film evaporator is 50-60 ml/min.
The preparation method of the TCPP flame retardant is characterized in that the vacuum requirement of primary molecular distillation is 10-30Pa, and preferably 10-20 Pa.
The preparation method of the TCPP flame retardant is characterized in that the temperature requirement of primary molecular distillation is 90-120 ℃, and preferably 100-110 ℃.
The preparation method of the TCPP flame retardant is characterized in that the feeding speed during primary molecular distillation is required to be 30-40ml/min, and the rotating speed of a scraper is required to be 250-280 r/min.
The preparation method of the TCPP flame retardant is characterized in that the vacuum requirement of secondary molecular distillation is 0-20Pa, and preferably 0-10 Pa.
The preparation method of the TCPP flame retardant is characterized in that the temperature requirement of the secondary molecular distillation is 120-150 ℃, and preferably 120-130 ℃.
The preparation method of the TCPP flame retardant is characterized in that the feeding speed during secondary molecular distillation is required to be 30-40ml/min, and the rotating speed of a scraper is required to be 250-280 r/min.
By adopting the process technology, compared with the prior art, the invention has the following advantages:
1) the method does not generate wastewater on the premise of not influencing the product yield and the acid value, and is more green and environment-friendly;
2) the content of aldehyde compounds in the TCPP finished product prepared by the method is less than 10ppm, and the smell is small;
3) the invention can also be used for preparing phosphate flame retardants prepared by reacting other epoxy compounds with phosphorus oxychloride, such as tris (chloroethyl) phosphate (TCPP for short).
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto.
Example 1:
preparing a TCPP crude product: adding 921g (6 mol) of phosphorus oxychloride and 2.7g of aluminum trichloride catalyst into a reaction device, heating to 60 ℃, then dripping 1075.32g (18.54 mol) of propylene oxide, keeping the reaction temperature unchanged in the dripping process, and keeping the temperature at 70 ℃ for 1 hour after dripping to obtain a crude product of TCPP.
Example 2:
1000g of the crude TCPP obtained in example 1 was taken and fed into a thin-film evaporator (vacuum 95Pa, temperature 120 ℃) at a feed rate of 60ml/min to remove most of the low-boiling components, and then fed into a primary molecular distillation (vacuum 12Pa, temperature 110 ℃) at a feed rate of 35ml/min to remove the remaining low-boiling components for the second time at a scraper speed of 250 rpm, and finally fed into a secondary molecular distillation (vacuum 5Pa, temperature 120 ℃) at a feed rate of 30ml/min to distill off the feed liquid at a scraper speed of 270 rpm, thereby obtaining the finished TCPP with a yield of 98.6%. Sampling to obtain an acid value of 0.02mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in the attached table 1.
Example 3:
1000g of the crude TCPP obtained in example 1 was taken and fed into a thin-film evaporator (vacuum 108Pa, temperature 115 ℃) at a feed rate of 55ml/min to remove most of the low-boiling components, and then fed into a primary molecular distillation (vacuum 12Pa, temperature 100 ℃) at a feed rate of 30ml/min to remove the remaining low-boiling components for the second time at a scraper speed of 270 rpm, and finally fed into a secondary molecular distillation (vacuum 8Pa, temperature 130 ℃) at a feed rate of 35ml/min at a scraper speed of 250 rpm, and the feed liquid was distilled off to obtain the finished TCPP with a yield of 98.7%. Sampling to obtain an acid value of 0.03mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in an attached table 1.
Example 4:
1000g of the crude TCPP obtained in example 1 was taken and fed into a thin film evaporator (vacuum 87Pa, temperature 120 ℃) at a feed rate of 50ml/min to remove most of the low-boiling components, and then fed into a primary molecular distillation (vacuum 10Pa, temperature 110 ℃) at a feed rate of 30ml/min to secondarily remove the remaining low-boiling components, wherein the scraper velocity was 265 rpm, and finally fed into a secondary molecular distillation (vacuum 5Pa, temperature 130 ℃) at a feed rate of 30ml/min to distill the feed liquid at 275 rpm, thereby obtaining the finished TCPP, and the yield was 98.4%. Sampling to obtain an acid value of 0.03mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in an attached table 1.
Example 5:
1000g of the crude TCPP obtained in example 1 was taken and fed into a thin-film evaporator (vacuum 90Pa, temperature 120 ℃) at a feed rate of 50ml/min to remove most of the low-boiling components, and then fed into a primary molecular distillation (vacuum 10Pa, temperature 100 ℃) at a feed rate of 35ml/min to remove the remaining low-boiling components for the second time at a scraper speed of 255 rpm, and finally fed into a secondary molecular distillation (vacuum 9Pa, temperature 140 ℃) at a feed rate of 40ml/min at a scraper speed of 265 rpm, and the feed liquid was distilled off to obtain the finished TCPP with a yield of 98.8%. Sampling to obtain an acid value of 0.04mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in the attached table 1.
Example 6:
1000g of the crude TCPP obtained in example 1 was taken and fed into a thin-film evaporator (vacuum 88Pa, temperature 120 ℃) at a feed rate of 55ml/min to remove most of the low-boiling components, and then fed into a primary molecular distillation (vacuum 13Pa, temperature 110 ℃) at a feed rate of 32ml/min to remove the remaining low-boiling components for the second time at a scraper speed of 280 rpm, and finally fed into a secondary molecular distillation (vacuum 6Pa, temperature 130 ℃) at a feed rate of 34ml/min at a scraper speed of 260 rpm, and the feed liquid was distilled off to obtain the finished TCPP with a yield of 98.6%. Sampling to obtain an acid value of 0.02mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in the attached table 1.
Example 7:
1000g of the crude TCPP obtained in example 1 was taken and fed into a thin-film evaporator (vacuum 140Pa, temperature 90 ℃) at a feed rate of 60ml/min to remove most of the low-boiling components, and then fed into a primary molecular distillation (vacuum 18Pa, temperature 90 ℃) at a feed rate of 40ml/min to remove the remaining low-boiling components for the second time at a scraper speed of 250 rpm, and finally fed into a secondary molecular distillation (vacuum 10Pa, temperature 120 ℃) at a feed rate of 30ml/min at a scraper speed of 280 rpm, and the feed liquid was distilled off to obtain the finished TCPP with a yield of 98.5%. Sampling to obtain an acid value of 0.04mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in the attached table 1.
Example 8:
1000g of the crude TCPP obtained in example 1 was taken and fed into a thin-film evaporator (vacuum 160Pa, temperature 130 ℃) at a feed rate of 60ml/min to remove most of the low-boiling components, and then fed into a primary molecular distillation (vacuum 14Pa, temperature 120 ℃) at a feed rate of 35ml/min to secondarily remove the remaining low-boiling components, wherein the scraper velocity was 270 rpm, and finally fed into a secondary molecular distillation (vacuum 6Pa, temperature 150 ℃) at a feed rate of 40ml/min to distill the feed liquid at 265 rpm, thereby obtaining the finished TCPP, and the yield was 98.6%. Sampling to obtain an acid value of 0.05mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in an attached table 1.
Example 9:
1000g of the crude TCPP obtained in example 1 was taken and fed into a thin-film evaporator (vacuum 130Pa, temperature 100 ℃) at a feed rate of 60ml/min to remove most of the low-boiling components, and then fed into a primary molecular distillation (vacuum 15Pa, temperature 100 ℃) at a feed rate of 35ml/min to remove the remaining low-boiling components for the second time at a scraper speed of 255 rpm, and finally fed into a secondary molecular distillation (vacuum 5Pa, temperature 130 ℃) at a feed rate of 30ml/min to distill off the feed liquid at 280 rpm, thereby obtaining the finished TCPP with a yield of 98.7%. Sampling to obtain an acid value of 0.03mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in an attached table 1. 1.
Example 10:
1000g of the crude TCPP obtained in example 1 was taken and fed into a thin-film evaporator (vacuum 80Pa, temperature 100 ℃) at a feed rate of 60ml/min to remove most of the low-boiling components, and then fed into a primary molecular distillation (vacuum 20Pa, temperature 100 ℃) at a feed rate of 35ml/min to remove the remaining low-boiling components for the second time at a scraper speed of 275 rpm, and finally fed into a secondary molecular distillation (vacuum 2Pa, temperature 130 ℃) at a feed rate of 30ml/min to distill off the feed liquid at a scraper speed of 255 rpm, and the finished TCPP was obtained with a yield of 98.8%. Sampling to obtain an acid value of 0.02mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in the attached table 1.
Example 11:
1000g of the crude TCPP obtained in example 1 was taken and fed into a thin-film evaporator (vacuum 120Pa, temperature 110 ℃) at a feed rate of 60ml/min to remove most of the low-boiling components, and then fed into a primary molecular distillation (vacuum 30Pa, temperature 90 ℃) at a feed rate of 35ml/min to remove the remaining low-boiling components for the second time at a scraper speed of 260 rpm, and finally fed into a secondary molecular distillation (vacuum 20Pa, temperature 140 ℃) at a feed rate of 30ml/min at a scraper speed of 255 rpm, and the feed liquid was distilled off to obtain the finished TCPP with a yield of 98.3%. Sampling to obtain an acid value of 0.04mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in the attached table 1.
Example 12:
1000g of the crude TCPP obtained in example 1 was taken and fed into a thin-film evaporator (vacuum 200Pa, temperature 110 ℃) at a feed rate of 60ml/min to remove most of the low-boiling components, and then fed into a primary molecular distillation (vacuum 30Pa, temperature 90 ℃) at a feed rate of 35ml/min to secondarily remove the remaining low-boiling components, wherein the scraper velocity was 250 rpm, and finally fed into a secondary molecular distillation (vacuum 20Pa, temperature 120 ℃) at a feed rate of 30ml/min to distill the feed liquid at 250 rpm, thereby obtaining the finished TCPP with a yield of 98.1%. Sampling to obtain an acid value of 0.03mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in an attached table 1.
Comparative example 1:
1000g of the crude TCPP prepared in example 1 was taken and put into a 2000ml four-necked flask equipped with a thermometer, 500g of water was added, the pH was adjusted to 8.0 with an alkali, the mixture was stirred at 80 ℃ for half an hour, and subjected to static liquid separation, the material layer was washed with water to neutrality, and subjected to static liquid separation, and the obtained hydrous material layer was dehydrated by distillation under reduced pressure (400 Pa, the kettle temperature was 120 ℃) to obtain a finished TCPP with a yield of 98.6%. Sampling to obtain an acid value of 0.03mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in an attached table 1.
Comparative example 2:
1000g of the crude TCPP prepared in example 1 was taken and put into a 2000ml four-necked flask equipped with a thermometer, 500g of water was added, the pH was adjusted to 8.0 with an alkali, the mixture was stirred at 80 ℃ for half an hour, and subjected to static liquid separation, the material layer was washed with water to neutrality, and subjected to static liquid separation, and the obtained hydrous material layer was dehydrated by distillation under reduced pressure (380 Pa, the kettle temperature was 120 ℃) to obtain a finished TCPP with a yield of 98.4%. Sampling to obtain an acid value of 0.04mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in the attached table 1.
Comparative example 3:
1000g of the crude TCPP prepared in example 1 was taken and put into a 2000ml four-necked flask equipped with a thermometer, 500g of water was added, the pH was adjusted to 8.0 with an alkali, the mixture was stirred at 80 ℃ for half an hour, and subjected to static liquid separation, the material layer was washed with water to neutrality, and subjected to static liquid separation, and the resulting hydrous material layer was dehydrated by distillation under reduced pressure (350 Pa, the pot temperature was 115 ℃) to obtain a finished TCPP with a yield of 98.7%. Sampling to obtain an acid value of 0.03mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in an attached table 1.
Comparative example 4:
1000g of the crude TCPP prepared in example 1 was taken and put into a 2000ml four-necked flask equipped with a thermometer, 500g of water was added, the pH was adjusted to 8.0 with an alkali, the mixture was stirred at 80 ℃ for half an hour, and subjected to static liquid separation, the material layer was washed with water to neutrality, and subjected to static liquid separation, and the resulting hydrous material layer was dehydrated by distillation under reduced pressure (420 Pa, the pot temperature was 120 ℃) to obtain a finished TCPP with a yield of 98.6%. Sampling to obtain an acid value of 0.02mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in the attached table 1.
Comparative example 5:
1000g of the crude TCPP prepared in example 1 was taken and put into a 2000ml four-necked flask equipped with a thermometer, 500g of water was added, the pH was adjusted to 8.0 with an alkali, the mixture was stirred at 80 ℃ for half an hour, and subjected to static liquid separation, the material layer was washed with water to neutrality, and subjected to static liquid separation, and the resulting hydrous material layer was dehydrated by distillation under reduced pressure (340 Pa, pot temperature distilled to 118 ℃) to obtain a finished TCPP with a yield of 98.5%. Sampling to obtain an acid value of 0.03mgKOH/g, and detecting the content of aldehyde compounds, wherein the detection results are shown in an attached table 1.
Compared with the comparative example, the example does not produce waste water, while the comparative example produces waste water in the processes of alkali washing and water washing, and the waste water needs to be treated in the later period. The invention is more environment-friendly. The detection results of the aldehyde compounds of each sample of TCPP are shown in the attached table 1:
table 1 results of detecting aldehydes in TCPP samples
| Sample (I) | Aldehyde compound (ppm) | Sample (I) | Aldehyde compound (ppm) |
| Example 2 | 5.3 | Comparative example 1 | 124.6 |
| Example 3 | 2.4 | Comparative example 2 | 112.4 |
| Example 4 | 3.7 | Comparative example 3 | 110.6 |
| Example 5 | 5.5 | Comparative example 4 | 130.6 |
| Example 6 | 2.6 | Comparative example 5 | 102.8 |
| Example 7 | 4.1 | ||
| Example 8 | 6.3 | ||
| Example 9 | 3.2 | ||
| Example 10 | 4.8 | ||
| Example 11 | 9.3 | ||
| Example 12 | 9.8 |
And (3) analyzing a detection result: as can be seen from the attached table 1, the aldehyde compound of the TCPP flame retardant prepared by the invention is less than 10ppm, and the content of the aldehyde compound is lower than that of the finished product of TCPP prepared by the prior art.
Claims (10)
1. A preparation method of TCPP fire retardant, including phosphorus oxychloride, under the catalysis of Lewis acid catalyst, react with propylene oxide to get TCPP crude product, characterized by that to evaporate most low-boiling-point substance under the vacuum condition through the film evaporator first crude product got in preparation, carry on the secondary removal to the rest low-boiling-point substance under the high vacuum condition through the first-order molecular distillation; finally, the material is distilled out under the condition of high vacuum through secondary molecular distillation, and the finished product of TCPP is obtained.
2. The process according to claim 1, wherein the vacuum requirement of the thin film evaporator is 80 to 200Pa, preferably 80 to 120 Pa.
3. The process for preparing TCPP flame retardant according to claim 1, wherein the temperature of the thin film evaporator is 90-130 ℃, preferably 100-120 ℃.
4. The process according to claim 1, wherein the feed rate to the thin film evaporator is 50-60 ml/min.
5. The process according to claim 1, wherein the vacuum requirement of the primary molecular distillation is 10-30Pa, preferably 10-20 Pa.
6. The process according to claim 1, wherein the temperature of the first molecular distillation is 90-120 ℃, preferably 100-110 ℃.
7. The method as claimed in claim 1, wherein the feeding speed of the first molecular distillation is 30-40ml/min, and the scraper rotation speed is 250-280 rpm.
8. The process according to claim 1, wherein the vacuum requirement of the secondary molecular distillation is 0-20Pa, preferably 0-10 Pa.
9. The method of claim 1, wherein the temperature of the secondary molecular distillation is 120-150 ℃, preferably 120-130 ℃.
10. The method as claimed in claim 1, wherein the feeding speed of the second-stage molecular distillation is 30-40ml/min, and the scraper rotation speed is 250-280 rpm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478620A (en) * | 2022-02-23 | 2022-05-13 | 淮安晨化新材料有限公司 | Preparation process of odorless phosphate flame retardant |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386732A (en) * | 2001-05-23 | 2002-12-25 | 郭贵明 | Process for extracting high-purity natural citral |
| CN101045785A (en) * | 2007-04-19 | 2007-10-03 | 中国林业科学研究院林产化学工业研究所 | Rosinpolyether polylol for hard polyurethane foam plastic and preparation method thereof |
| CN101205194A (en) * | 2007-12-10 | 2008-06-25 | 吴贵岚 | Three-stage continuous separation and purification technique of fatty primary amide |
| CN102002068A (en) * | 2010-11-29 | 2011-04-06 | 浙江万盛化工有限公司 | After-treatment method of crude tris-(2-isopropyl chloride) phosphate |
| CN102206141A (en) * | 2011-04-11 | 2011-10-05 | 浙江大学 | Molecular distillation separation method of bio-oil |
| CN102417447A (en) * | 2011-10-31 | 2012-04-18 | 广西亿康药业股份有限公司 | Production method of undecylenic acid |
| CN106496264A (en) * | 2016-09-27 | 2017-03-15 | 浙江万盛股份有限公司 | A kind of bisphenol-A is double（Diphenyl phosphoester）Continuous preparation method |
| CN106543427A (en) * | 2016-11-01 | 2017-03-29 | 万华化学集团股份有限公司 | Volatile material the method that reduces abnormal smells from the patient in a kind of removing polyether polyol |
| CN106565773A (en) * | 2016-11-11 | 2017-04-19 | 泰州新安阻燃材料有限公司 | Preparation method of high-purity tris(clorisopropyl) phosphate as phosphate flame retardant |
| CN108794522A (en) * | 2018-05-07 | 2018-11-13 | 浙江万盛股份有限公司 | A kind of tricresyl phosphate（The chloro- 2- propyl of 1-）The Total continuity stream production technology of ester |
| CN108929225A (en) * | 2018-06-30 | 2018-12-04 | 浙江工业大学 | A kind of methyl formylcaprylate isolation and purification method |
| CN109912644A (en) * | 2019-04-09 | 2019-06-21 | 浙江万盛股份有限公司 | A kind of post-processing purifying technique of TCPP production crude product |
| CN110642826A (en) * | 2019-09-05 | 2020-01-03 | 江西省科学院应用化学研究所 | Method for extracting vitamin E from tea oil deodorized distillate by using molecular distillation technology |
| CN110862531A (en) * | 2019-12-17 | 2020-03-06 | 句容宁武新材料股份有限公司 | Combined device for removing low-boiling-point substances in polyether |
-
2020
- 2020-10-20 CN CN202011125568.8A patent/CN112209964B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386732A (en) * | 2001-05-23 | 2002-12-25 | 郭贵明 | Process for extracting high-purity natural citral |
| CN101045785A (en) * | 2007-04-19 | 2007-10-03 | 中国林业科学研究院林产化学工业研究所 | Rosinpolyether polylol for hard polyurethane foam plastic and preparation method thereof |
| CN101205194A (en) * | 2007-12-10 | 2008-06-25 | 吴贵岚 | Three-stage continuous separation and purification technique of fatty primary amide |
| CN102002068A (en) * | 2010-11-29 | 2011-04-06 | 浙江万盛化工有限公司 | After-treatment method of crude tris-(2-isopropyl chloride) phosphate |
| CN102206141A (en) * | 2011-04-11 | 2011-10-05 | 浙江大学 | Molecular distillation separation method of bio-oil |
| CN102417447A (en) * | 2011-10-31 | 2012-04-18 | 广西亿康药业股份有限公司 | Production method of undecylenic acid |
| CN106496264A (en) * | 2016-09-27 | 2017-03-15 | 浙江万盛股份有限公司 | A kind of bisphenol-A is double（Diphenyl phosphoester）Continuous preparation method |
| CN106543427A (en) * | 2016-11-01 | 2017-03-29 | 万华化学集团股份有限公司 | Volatile material the method that reduces abnormal smells from the patient in a kind of removing polyether polyol |
| CN106565773A (en) * | 2016-11-11 | 2017-04-19 | 泰州新安阻燃材料有限公司 | Preparation method of high-purity tris(clorisopropyl) phosphate as phosphate flame retardant |
| CN108794522A (en) * | 2018-05-07 | 2018-11-13 | 浙江万盛股份有限公司 | A kind of tricresyl phosphate（The chloro- 2- propyl of 1-）The Total continuity stream production technology of ester |
| CN108929225A (en) * | 2018-06-30 | 2018-12-04 | 浙江工业大学 | A kind of methyl formylcaprylate isolation and purification method |
| CN109912644A (en) * | 2019-04-09 | 2019-06-21 | 浙江万盛股份有限公司 | A kind of post-processing purifying technique of TCPP production crude product |
| CN110642826A (en) * | 2019-09-05 | 2020-01-03 | 江西省科学院应用化学研究所 | Method for extracting vitamin E from tea oil deodorized distillate by using molecular distillation technology |
| CN110862531A (en) * | 2019-12-17 | 2020-03-06 | 句容宁武新材料股份有限公司 | Combined device for removing low-boiling-point substances in polyether |
Non-Patent Citations (1)
| Title |
|---|
| 高锦明等: "《天然产品加工工艺学》", 31 March 2018, 西北农林科技大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478620A (en) * | 2022-02-23 | 2022-05-13 | 淮安晨化新材料有限公司 | Preparation process of odorless phosphate flame retardant |
| CN114478620B (en) * | 2022-02-23 | 2024-03-22 | 淮安晨化新材料有限公司 | Preparation process of odorless phosphate flame retardant |
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