CN112143027B - Flame-retardant plasticizer containing phosphate triester compound and 3,5, 6-trichloropyridine-2-alcohol compound and preparation thereof - Google Patents
Flame-retardant plasticizer containing phosphate triester compound and 3,5, 6-trichloropyridine-2-alcohol compound and preparation thereof Download PDFInfo
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- CN112143027B CN112143027B CN202010901278.1A CN202010901278A CN112143027B CN 112143027 B CN112143027 B CN 112143027B CN 202010901278 A CN202010901278 A CN 202010901278A CN 112143027 B CN112143027 B CN 112143027B
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- trichloropyridine
- phosphite
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- -1 phosphate triester compound Chemical class 0.000 title claims abstract description 55
- 239000004014 plasticizer Substances 0.000 title claims abstract description 49
- 239000003063 flame retardant Substances 0.000 title claims abstract description 37
- 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 36
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 22
- 239000010452 phosphate Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000006184 cosolvent Substances 0.000 claims abstract description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 44
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- WCYYAQFQZQEUEN-UHFFFAOYSA-N 3,5,6-trichloropyridine-2-one Chemical compound ClC=1C=C(Cl)C(=O)NC=1Cl WCYYAQFQZQEUEN-UHFFFAOYSA-N 0.000 claims description 17
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 claims description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 claims description 2
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 3
- 150000005691 triesters Chemical class 0.000 abstract description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 10
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical compound O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- DXEYVFFFVOFVOK-UHFFFAOYSA-N sodium;3,5,6-trichloro-1h-pyridin-2-one Chemical compound [Na].ClC=1C=C(Cl)C(=O)NC=1Cl DXEYVFFFVOFVOK-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a flame retardant plasticizer containing a phosphate triester compound and a 3,5, 6-trichloropyridine-2-alcohol compound and a preparation method thereof, wherein the flame retardant plasticizer is mainly prepared from the following components in parts by weight: 60-90 parts of phosphoric triester compound, 10-39.5 parts of 3,5, 6-trichloropyridine-2-alcohol compound and 1-20 parts of cosolvent. The plasticizer provided by the invention has good intermiscibility, is convenient to use, has plasticity and flame retardance, is good in weather resistance and low in cost, and solves the problems that byproducts of (phosphite) triester products are difficult to treat in the production process, the purification cost of target products is high, three wastes are more, the separation is difficult, and the like.
Description
Technical Field
The invention belongs to the technical field of flame retardant plasticizers, and particularly relates to a flame retardant plasticizer containing a phosphate triester compound and a 3,5, 6-trichloropyridine-2-alcohol compound and a preparation method thereof.
Background
At present, the fire safety situation is more and more strict, the fire standard and the requirement of plastics for cables, wires and electric appliances are more and more strict, the fire protection requirements of places and industries such as families, offices, restaurants, hotels, warehouses, workshops and the like are more and more intense, and the bromine-containing fire retardant has higher toxicity and higher bromine cost.
The phosphotriester compounds, such as (phosphorous) phosphotriester, have good plasticizing performance, but low flame retardant efficiency and high volatility, and by-products (containing isomers) generated in the synthesis of (phosphorous) phosphotriester products are more, separation and purification procedures such as extraction, rectification, refining and the like are required, organic solvents are required in the purification, and devices such as rectification, purification and the like are required to be matched, so that the equipment investment is high, the energy consumption is high, the operation procedures are more, the cost and the difficulty of the treatment of 'three wastes' are increased, the potential safety hazard is increased in the purification process, and the cost is greatly increased.
Disclosure of Invention
The invention aims to provide a flame-retardant plasticizer containing a phosphate triester compound and a 3,5, 6-trichloropyridine-2-alcohol compound on the basis of the prior art, wherein the phosphate triester compound and the 3,5, 6-trichloropyridine-2-alcohol compound are used as main raw materials, so that the problems of difficulty in treating byproducts, high purification cost of target products, more three wastes, difficulty in separation and the like in the production process of (sub) phosphate triester products are solved, and the potential safety hazard of separation and purification of the (sub) phosphate triester byproducts (containing isomers) is avoided; the application of the 3,5, 6-trichloropyridine-2-alcohol compound is widened, and the economic, environmental protection and social benefits are increased.
Another object of the present invention is to provide a method for preparing the flame retardant plasticizer containing the above-mentioned phosphotriester compound and 3,5, 6-trichloropyridin-2-ol compound.
The technical scheme of the invention is as follows:
a flame-retardant plasticizer containing a phosphate triester compound and a 3,5, 6-trichloropyridine-2-alcohol compound is mainly prepared from the following components in parts by weight: 60-90 parts of phosphoric triester compounds, 10-39.5 parts of 3,5, 6-trichloropyridine-2-alcohol compounds and 1-20 parts of cosolvent.
In a preferred scheme, the flame retardant plasticizer containing the phosphate triester compound and the 3,5, 6-trichloropyridin-2-ol compound provided by the invention is mainly prepared from the following components in parts by weight: 60-67 parts of phosphoric triester compounds, 25-30 parts of 3,5, 6-trichloropyridine-2-alcohol compounds and 4-15 parts of cosolvent.
The phosphoric triester compound refers to phosphoric triester, diester and sub-state compounds thereof and other byproducts prepared by the esterification reaction of phosphorus oxychloride and aliphatic alcohol or aromatic alcohol, and can be but is not limited to one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, trioctyl phosphite or triphenyl phosphite; and the target products, isomers and by-products obtained in the process of producing the above compounds.
In a preferred embodiment, the phosphoric acid triester compound is one or more of trimethyl phosphate, trioctyl phosphate, trimethyl phosphite or trioctyl phosphite, for example, trimethyl phosphate, trimethyl phosphite, and target products, isomers and by-products obtained in the process of producing trimethyl phosphate or trimethyl phosphite.
For the present invention, the 3,5, 6-trichloropyridin-2-ol compound is 3,5, 6-trichloropyridin-2-ol and metal salts such as potassium salt and sodium salt thereof, and other derivatives derived from 3,5, 6-trichloropyridin-ol as a main raw material.
In a preferable scheme, the 3,5, 6-trichloropyridin-2-ol compound is 3,5, 6-trichloropyridin-2-ol which is a common chemical, has stable chemical property, high melting point (169-171 ℃), low toxicity (slight toxicity), difficult combustion, moderate price and easily obtained raw materials.
The phosphoric triester compound has good plasticizing performance and intermiscibility, but the flame retardant performance is not good. The plasticizer prepared by compounding the phosphoric acid triester compound and the 3,5, 6-trichloropyridine-2-alcohol compound serving as main raw materials has good flame retardance and plasticity, complementary advantages, good exertion of plasticity and flame retardance, moderate price, high cost performance and wide application.
For the purposes of the present invention, the cosolvent is a high boiling point inert solvent which does not react with the phosphoric acid triester compound and the 3,5, 6-trichloropyridin-2-ol compound, but can enhance the dispersibility and solubility of the 3,5, 6-trichloropyridin-2-ol compound in the phosphoric acid triester compound, and can be, but is not limited to, dimethylformamide (DMF) or Dimethylsulfoxide (DMSO), and in a preferred embodiment, the flame retardant plasticizer containing the phosphoric acid triester compound and the 3,5, 6-trichloropyridin-2-ol compound is mainly prepared from the following components in parts by weight: 60 to 66.7 portions of trimethyl phosphate, 25 to 29.2 portions of 3,5, 6-trichloropyridine-2-alcohol and 4.1 to 15 portions of dimethylformamide or dimethyl sulfoxide.
In a preferable scheme, the flame retardant plasticizer containing the phosphate triester compound and the 3,5, 6-trichloropyridine-2-alcohol compound is mainly prepared from the following components in parts by weight: trimethyl phosphite 66.7 weight portions, 3,5, 6-trichloropyridine-2-alcohol 29.2 weight portions, and dimethyl sulfoxide 4.1 weight portions.
In a preferable scheme, the flame retardant plasticizer containing the phosphate triester compound and the 3,5, 6-trichloropyridine-2-alcohol compound is mainly prepared from the following components in parts by weight: 66.7 parts of a mixture containing trimethyl phosphate and trimethyl phosphite, 29.2 parts of 3,5, 6-trichloropyridin-2-ol and 4.1 parts of dimethyl sulfoxide.
In a preferable scheme, the flame retardant plasticizer containing the phosphate triester compound and the 3,5, 6-trichloropyridine-2-alcohol compound is mainly prepared from the following components in parts by weight: 66.7 parts of a mixture containing trioctyl phosphate and trioctyl phosphite, 29.2 parts of 3,5, 6-trichloropyridin-2-ol and 4.1 parts of dimethyl sulfoxide.
The invention also provides a preparation method of the flame retardant plasticizer containing the phosphate triester compound and the 3,5, 6-trichloropyridine-2-alcohol compound, which comprises the following steps: after the phosphoric triester compound and the cosolvent are stirred and mixed uniformly, the 3,5, 6-trichloropyridine-2-alcohol compound is added in the stirring process, and the mixture is stirred and mixed uniformly.
In a preferred scheme, when the phosphoric acid triester compound and the cosolvent are uniformly stirred and mixed, the stirring speed is controlled to be 60-100 revolutions per minute; preferably 80 rpm.
In a preferable scheme, after 3,5, 6-trichloropyridine-2-alcohol compounds are added, the stirring speed is controlled to be 120-150 r/m; preferably 130 rpm.
By adopting the technical scheme of the invention, the advantages are as follows:
(1) The plasticizer is prepared by compounding the phosphoric acid triester compound and the 3,5, 6-trichloropyridine-2-alcohol compound serving as main raw materials, has good intermiscibility, is convenient to use, has plasticity and flame retardance, is good in weather resistance, high in flash point, less in heating decrement, good in pipe, plate and wire formability and low in toxicity.
(2) The cost performance is high. The triester phosphate compound selected by the invention has low price, and the plasticizer prepared by compounding the triester phosphate compound with the 3,5, 6-trichloropyridine-2-alcohol compound improves the flame retardance, can normally exert the plasticity and weather resistance of the triester phosphate compound, and brings out the best in the flame retardance and the plasticity.
(3) The application range is wider. The plasticizer prepared from the phosphoric triester compound has poor flame retardant efficiency and is limited in the field of high flame retardant application, and after the plasticizer is compounded with the 3,5, 6-trichloropyridine-2-alcohol compound with low price, the flame retardant property of the plasticizer is greatly enhanced, the application range is wider, the cost is lower than that of the phosphoric triester compound with a single component, and the use and manufacturing normality of the plasticizer is not changed.
(4) The invention widens the application field of the phosphoric acid triester compound and the 3,5, 6-trichloropyridine-2-alcohol compound. Particularly, the composite flame-retardant plasticizer can be prepared from main products of the phosphoric acid triesters and the phosphorous acid triesters and byproducts generated in the synthetic process without purification and separation, thereby reducing the potential safety hazard and the environmental protection risk of upstream raw material suppliers and having better economic and social benefits.
Detailed Description
The flame retardant plasticizer of the present invention is further illustrated by the following examples, but the present invention is not limited to these examples.
Example 1
A flame-retardant plasticizer containing a phosphate triester compound and a 3,5, 6-trichloropyridin-2-ol compound is prepared by a method comprising the steps of:
(1) A1.5L three-mouth glass flask is fixed on an iron support, the bottom of the flask is stabilized by an asbestos electric heating sleeve, and the flask is connected with an electric stirring and feeding funnel.
(2) 600g of trimethyl phosphate, 150g of dimethyl sulfoxide and 250g of 3,5, 6-trichloropyridin-2-ol are accurately weighed in a flask with marks.
(3) Sequentially adding the weighed trimethyl phosphate and dimethyl sulfoxide through a funnel, starting electric stirring, and controlling the rotating speed to be 80 r/m.
(4) Under the stirring state, weighed 3,5, 6-trichloropyridine-2-alcohol is added through a funnel, after the addition is finished, a burr glass plug is covered, and the stirring speed is adjusted to 130 r/min.
(5) Stirring was stopped until the contents of the three-necked flask were mixed well (about 15 minutes).
(6) And (6) pouring the material obtained in the step (5) into a prepared suction filtration barrel for vacuum suction filtration to obtain a clear and transparent finished product.
Example 2
(2) 667g of trimethyl phosphate, 41g of dimethylformamide, and 292g of 3,5, 6-trichloropyridin-2-ol were weighed accurately in a flask already labeled, and the other steps were the same as in example 1.
Example 3
(2) 667g of trimethyl phosphite, 41g of dimethyl sulfoxide, and 292g of 3,5, 6-trichloropyridin-2-ol were weighed accurately in the flask already labeled, and the other steps were the same as in example 1.
Example 4
(2) In a flask equipped with a stopper, 667g of crude trimethyl phosphate, 41g of dimethyl sulfoxide and 292g of 3,5, 6-trichloropyridin-2-ol were prepared, and the other steps were carried out in the same manner as in example 1. For this example, the crude trimethyl phosphate is a mixture of trimethyl phosphate, trimethyl phosphite and other related impurities obtained after the reaction is completed and methanol is removed.
Example 5
(2) The same procedures as in example 1 were repeated except that 667g of crude trioctyl phosphate, 41g of dimethyl sulfoxide and 292g of 3,5, 6-trichloropyridin-2-ol were accurately placed in the flask already identified. For this example, the trioctyl phosphate crude product is a mixture containing trioctyl phosphate, trioctyl phosphite and other related impurities obtained after the reaction is completed and methanol is removed.
Example 6
(2) 667g of trimethyl phosphate, 41g of dimethylformamide, and 292g of sodium 3,5, 6-trichloropyridin-2-ol were weighed accurately in the flask already labeled, and the other steps were the same as in example 1.
Example 7
(2) 667g of trimethyl phosphite, 41g of dimethyl sulfoxide, and 292g of sodium 3,5, 6-trichloropyridin-2-ol were weighed accurately in a flask already labeled, and the other steps were the same as in example 1.
Example 8
(2) In a flask equipped with a stopper, 667g of crude trimethyl phosphate, 41g of dimethyl sulfoxide, and 292g of sodium 3,5, 6-trichloropyridin-2-ol were prepared, and the other steps were the same as in example 1. For this example, the crude trimethyl phosphate is a mixture of trimethyl phosphate, trimethyl phosphite and other related impurities obtained after the reaction is completed and methanol is removed.
Example 9
(2) The same procedures as in example 1 were repeated except that 667g of crude trioctyl phosphate, 41g of dimethyl sulfoxide and 292g of 3,5, 6-trichloropyridin-2-ol were accurately placed in the flask already identified. For this example, when the crude trioctyl phosphate is trioctyl phosphate, the reaction is completed, and methanol is removed to obtain a mixture containing trioctyl phosphate, trioctyl phosphite, and other related impurities.
Comparative example 1
A flame-retardant plasticizer containing a phosphate triester compound is prepared by the following steps:
(1) A1.5L three-mouth glass flask is fixed on an iron support, the bottom of the flask is stabilized by an asbestos electric heating sleeve, and the flask is connected with an electric stirring and feeding funnel.
(2) In the identified flask, 150g of crude trimethyl phosphate 959 and dimethyl sulfoxide were accurately weighed.
(3) Sequentially adding the weighed trimethyl phosphate and dimethyl sulfoxide into the flask through a funnel, starting electric stirring, controlling the rotating speed to be 80 rpm, and stopping stirring after the materials in the three-neck flask are uniformly mixed (about 15 minutes).
(4) And (4) pouring the material obtained in the step (3) into a prepared suction filtration barrel for vacuum suction filtration to obtain a clear and transparent finished product.
For this comparative example, the crude trimethyl phosphate was the resulting mixture of trimethyl phosphate, trimethyl phosphite and other related impurities after the reaction was completed and methanol was removed during the production of trimethyl phosphate.
Comparative example 2
(2) 867g of crude trimethyl phosphate, 41g of dimethyl sulfoxide and 92g of 3,5, 6-trichloropyridin-2-ol were added to the flask so identified, and the other steps were the same as in example 1. For this comparative example, the crude trimethyl phosphate was the resulting mixture of trimethyl phosphate, trimethyl phosphite and other related impurities after the reaction was completed and methanol was removed during the production of trimethyl phosphate.
Performance analysis of flame retardant plasticization prepared by the invention in PVC
Taking example 4 as an example (replacing with the code TLCP), the performance analysis of the flame retardant plasticity in PVC of the invention I, the experimental part,
1. Main raw materials
①PVC：S-1000；
(2) Filling agent: caC0 3 ；
(3) A calcium zinc stabilizer;
(4) plasticizer I: DOP (dioctyl phthalate);
(5) and (3) a plasticizer II: DOTP (dioctyl terephthalate);
(6) plasticizer III: (homemade, TLCP, inventive example 4 formulation)
2. Main apparatus and equipment
(1) Biaxial plastic refining machine: SK-160B;
(2) a plate vulcanizing machine: XLB-D350X 2;
(3) electric heat forced air drying cabinet: HG101-1A;
(4) microcomputer control electronic universal tester: CMT5254;
(5) analytical electronic balance: an FA1004;
(6) melt flow rate meter: XNB-400A;
(7) high resistance meter: ZC36;
(8) oxygen index determinator: HC-2;
3. sample preparation:
the preparation method of the sample comprises the steps of accurately weighing 100g of PVC resin, 30g of filler and 2.8g of calcium-zinc stabilizer according to the mixture ratio, respectively weighing 10g of plasticizer I (DOP), plasticizer II (DOP), plasticizer III (self-made formula, TLCP, formula 4 in the invention), plasticizer VI (formula in comparative example 1) and plasticizer V (formula in comparative example 2), respectively, uniformly mixing the plasticizer I, the plasticizer II and the plasticizer III with the PVC resin, the filler and the calcium-zinc stabilizer, forming a plurality of contrast samples, respectively performing pre-plasticization, mixing for 15min at 150 ℃ on a biaxial plasticator, discharging, cutting into small pieces, putting the small pieces into a die, pressing into a film with the thickness of 1mm at 148 ℃ on a flat vulcanizing machine, respectively pressurizing step by step with the pressures of 1mPa, 5mPa and 10mPa, respectively performing hot pressing for 3min,3min and 5min, then performing cold pressing for 5min, respectively placing the samples for 24h, and cutting and preparing the samples.
4. Testing
(1) Testing mechanical properties, namely testing tensile strength, elongation at break, 100% stress at definite elongation and permanent deformation according to GB/T1004-2006; the tear strength was determined according to GB/T529-2008.
(2) And (3) testing heat resistance: according to GB/T7141-2008, the prepared wafer sample with the diameter of about 23mm and the thickness of 1mm is heated and cooled to room temperature at the temperature of 140 ℃, and then the sample is weighed, and the weight loss percentage of the sample is calculated.
(3) And (3) testing electrical properties: testing according to the GB/T1692-2008 method.
(4) And (3) testing the fluidity: according to GB/T3682.1-2018, the load is 10kg at 180 ℃.
(5) The limiting oxygen index performance is tested according to GB/T2406.2-2009.
2. Results and discussion
1. Mechanical properties, as shown in Table 1
TABLE 1 mechanical Properties data
As can be seen from Table 1, by combining the mechanical performance of the three systems, the TLCP plasticizing system of the invention has good performance in the aspects of tensile strength, elongation at break and tear strength, and most of the data is between DOP and DOTP.
2. Heat resistance, as shown in Table 2
TABLE 2 Heat resistance data
As can be seen from Table 2 above, TLCP according to the present invention is superior to DOP and DOTP in heat resistance.
3. Electrical Properties, as shown in Table 3
Table 3 electrical property data
As can be seen from Table 3 above, the TLCP of the present invention has poorer electrical properties than DOP and DOTP, indicating better insulation properties.
4. Fluidity, as shown in Table 4
Table 4 flowability data
| Test item | Fluidity (g/10 min) |
| PVC/DOP | 12.22 |
| PVC/DOTP | 13.87 |
| PVC/TLCP | 13.53 |
| PVC/comparative example 1 | 13.11 |
| PVC/comparative example 2 | 13.62 |
As can be seen from Table 4 above, the TLCP of the present invention is superior in flowability.
5. Limiting oxygen index
As can be seen from the following table 5, the TLCP has the limit oxygen index of 39.53 percent and is proved to have excellent flame retardant property by the test according to the method of national standard GB/T2406-2009.
TABLE 5 limiting oxygen index
| Test item | Limiting oxygen index% |
| PVC/DOP | 23.41 |
| PVC/DOTP | 26.75 |
| PVC/DOTP | 39.53 |
| PVC/comparative example 1 | 25.48 |
| PVC/comparative example 2 | 32.14 |
Other embodiments, for example: the plasticizers prepared in example 1, example 2, example 3, example 5, example 6, example 7, example 8 and example 9 have similar effects to those of example 4 in terms of mechanical properties, heat resistance, electrical properties, fluidity and flame retardancy.
Of the two comparative examples listed in the present invention, comparative example 1 lacks 442g of 3,5, 6-trichloropyridin-2-ol as compared to example 4; comparative example 2 the amount of crude trimethyl phosphate was increased and the amount of 3,5, 6-trichloropyridin-2-ol was decreased. The plasticizer prepared in comparative examples 1 to 2 was inferior to that of example 4 of the present invention in all of mechanical properties, heat resistance, electrical properties, fluidity and flame retardancy.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: modifications of the technical solutions described in the foregoing embodiments are still possible, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. The flame-retardant plasticizer containing the phosphate triester compound and the 3,5, 6-trichloropyridine-2-alcohol compound is characterized by mainly comprising the following components in parts by weight: 60-90 parts of phosphoric triester compounds, 10-39.5 parts of 3,5, 6-trichloropyridine-2-alcohol compounds and 1-20 parts of cosolvent; wherein the phosphoric triester compound is one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, trioctyl phosphite or triphenyl phosphite; the 3,5, 6-trichloropyridine-2-alcohol compound is one or more of 3,5, 6-trichloropyridine-2-alcohol, 3,5, 6-trichloropyridine-2-sodium alcoholate or 3,5, 6-trichloropyridine-2-potassium alcoholate; the cosolvent is dimethylformamide or dimethyl sulfoxide.
2. A flame retardant plasticizer according to claim 1, which is mainly prepared from the following components in parts by weight: 60-67 parts of phosphoric triester compounds, 25-30 parts of 3,5, 6-trichloropyridine-2-alcohol compounds and 4-15 parts of cosolvent.
3. A flame retardant plasticizer according to claim 1 or 2, wherein said triester phosphate compound is one or more selected from the group consisting of trimethyl phosphate, trioctyl phosphate, trimethyl phosphite and trioctyl phosphite.
4. The flame retardant plasticizer according to claim 1 or 2, wherein said 3,5, 6-trichloropyridin-2-ol compound is 3,5, 6-trichloropyridin-2-ol.
5. A flame retardant plasticizer according to claim 1 or 2, which is mainly prepared from the following components in parts by weight: 60 to 66.7 parts of trimethyl phosphate, 25 to 29.2 parts of 3,5, 6-trichloropyridine-2-alcohol and 4.1 to 15 parts of dimethylformamide or dimethyl sulfoxide.
6. A flame retardant plasticizer according to claim 1 or 2, which is mainly prepared from the following components in parts by weight: 66.7 parts of trimethyl phosphite, 29.2 parts of 3,5, 6-trichloropyridine-2-alcohol and 4.1 parts of dimethyl sulfoxide.
7. A flame retardant plasticizer according to claim 1 or 2, which is mainly prepared from the following components in parts by weight: 66.7 parts of a mixture containing trimethyl phosphate and trimethyl phosphite, 29.2 parts of 3,5, 6-trichloropyridin-2-ol and 4.1 parts of dimethyl sulfoxide.
8. A flame retardant plasticizer according to claim 1 or 2, which is mainly prepared from the following components in parts by weight: 66.7 parts of a mixture containing trioctyl phosphate and trioctyl phosphite, 29.2 parts of 3,5, 6-trichloropyridin-2-ol and 4.1 parts of dimethyl sulfoxide.
9. The method for preparing a flame retardant plasticizer containing a triester phosphate compound and a 3,5, 6-trichloropyridin-2-ol compound according to claim 1, comprising the steps of: after the phosphoric triester compound and the cosolvent are stirred and mixed uniformly, the 3,5, 6-trichloropyridine-2-alcohol compound is added in the stirring process, and the mixture is stirred and mixed uniformly.
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|---|---|---|---|---|
| FR2239945A2 (en) * | 1973-08-06 | 1975-03-07 | Dynachim Sarl | Insecticidal compsn. for domestic animals - contg. dimethyl trichloro pyridylphosphate and supported on a substrate (e.g. a collar) |
| US4016225A (en) * | 1973-05-21 | 1977-04-05 | The Dow Chemical Company | Process for preparing phosphorothioates and phenylphosphonothioates |
| US4327216A (en) * | 1979-11-30 | 1982-04-27 | Ciba-Geigy Corporation | Process for producing 2,3,5,6-tetrachloropyridine and 3,5,6-trichloropyridin-2-ol |
| US5017705A (en) * | 1988-05-11 | 1991-05-21 | Luxembourg Industries (Pamol) Ltd. | Production of 3,5,6-trichloropyridin-2 ol and novel intermediates thereof |
| US5120846A (en) * | 1990-06-13 | 1992-06-09 | Dowelanco | Process for preparing phosphorothioates and phosphonoates in a three-phase system |
| CN109796748A (en) * | 2019-02-15 | 2019-05-24 | 美瑞新材料股份有限公司 | A kind of flame-retardant and anti-static thermoplastic polyurethane elastomer and its preparation method and application |
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2020
- 2020-09-01 CN CN202010901278.1A patent/CN112143027B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4016225A (en) * | 1973-05-21 | 1977-04-05 | The Dow Chemical Company | Process for preparing phosphorothioates and phenylphosphonothioates |
| FR2239945A2 (en) * | 1973-08-06 | 1975-03-07 | Dynachim Sarl | Insecticidal compsn. for domestic animals - contg. dimethyl trichloro pyridylphosphate and supported on a substrate (e.g. a collar) |
| US4327216A (en) * | 1979-11-30 | 1982-04-27 | Ciba-Geigy Corporation | Process for producing 2,3,5,6-tetrachloropyridine and 3,5,6-trichloropyridin-2-ol |
| US5017705A (en) * | 1988-05-11 | 1991-05-21 | Luxembourg Industries (Pamol) Ltd. | Production of 3,5,6-trichloropyridin-2 ol and novel intermediates thereof |
| US5120846A (en) * | 1990-06-13 | 1992-06-09 | Dowelanco | Process for preparing phosphorothioates and phosphonoates in a three-phase system |
| CN109796748A (en) * | 2019-02-15 | 2019-05-24 | 美瑞新材料股份有限公司 | A kind of flame-retardant and anti-static thermoplastic polyurethane elastomer and its preparation method and application |
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