CN117209531A - Preparation method of dialkyl aluminum phosphinate with different alkyl groups - Google Patents
Preparation method of dialkyl aluminum phosphinate with different alkyl groups Download PDFInfo
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- CN117209531A CN117209531A CN202311135433.3A CN202311135433A CN117209531A CN 117209531 A CN117209531 A CN 117209531A CN 202311135433 A CN202311135433 A CN 202311135433A CN 117209531 A CN117209531 A CN 117209531A
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- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 56
- ZJKCITHLCNCAHA-UHFFFAOYSA-K aluminum dioxidophosphanium Chemical compound [Al+3].[O-][PH2]=O.[O-][PH2]=O.[O-][PH2]=O ZJKCITHLCNCAHA-UHFFFAOYSA-K 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000001336 alkenes Chemical class 0.000 claims abstract description 69
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 65
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 64
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims abstract description 49
- 239000002244 precipitate Substances 0.000 claims abstract description 38
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000007259 addition reaction Methods 0.000 claims abstract description 21
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 150000003254 radicals Chemical class 0.000 claims abstract description 11
- 230000000977 initiatory effect Effects 0.000 claims abstract description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- -1 alkali metal salt Chemical class 0.000 claims description 13
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 11
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 150000002978 peroxides Chemical group 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003063 flame retardant Substances 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910001376 inorganic hypophosphite Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- RBUNRLBCSKCWSF-UHFFFAOYSA-M [PH2]([O-])=O.C(CCC)[Al+]CCCC Chemical compound [PH2]([O-])=O.C(CCC)[Al+]CCCC RBUNRLBCSKCWSF-UHFFFAOYSA-M 0.000 description 1
- WVLAZEHCUADXTN-UHFFFAOYSA-K aluminum butyl(ethyl)phosphinate Chemical compound [Al+3].CCCCP([O-])(=O)CC.CCCCP([O-])(=O)CC.CCCCP([O-])(=O)CC WVLAZEHCUADXTN-UHFFFAOYSA-K 0.000 description 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- KTLIMPGQZDZPSB-UHFFFAOYSA-M diethylphosphinate Chemical compound CCP([O-])(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-M 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Abstract
The application discloses a preparation method of dialkyl aluminum phosphinate with different alkyl groups, which comprises the following steps: (1) Dispersing aluminum hypophosphite solid in a solvent system containing alkali metal hydroxide and water in a low concentration, enabling olefin 1 and the aluminum hypophosphite solid to undergo an addition reaction at 100-150 ℃ and 0.1-0.3 MPa under the initiation of a free radical initiator, controlling the consumption of the olefin 1 until the aluminum hypophosphite solid fully reacts, preparing a monoalkyl aluminum phosphinate solution, filtering a precipitate, and collecting filtrate; (2) Continuously introducing olefin 2 different from olefin 1 into the filtrate, and enabling the aluminum monoalkylphosphinate and olefin 2 to undergo an addition reaction at 100-150 ℃ and 0.1-0.3 MPa under the initiation of a free radical initiator to obtain aluminum dialkylphosphinate precipitates with different alkyl groups. The purity of the dialkyl phosphinate aluminum with different alkyl groups prepared by the application is more than 99.5 percent.
Description
Technical Field
The application relates to the technical field of preparation of aluminum dialkylphosphinate, in particular to a preparation method of aluminum dialkylphosphinate with different alkyl groups, which can obtain high-purity aluminum dialkylphosphinate with different alkyl groups, has lower corrosiveness and can be used as a high polymer material flame retardant.
Background
The organic aluminum hypophosphite flame retardant has high phosphorus content and good flame retardance, and simultaneously has high hydrophobicity and thermal decomposition temperature which are greatly improved compared with inorganic hypophosphite due to the introduction of alkyl in a molecular structure, so that the organic aluminum hypophosphite flame retardant can not migrate and absorb moisture when being applied to a high polymer material, can resist high processing temperature, can not cause the reduction of the insulating property of the material, has good compatibility with matrix resin, and can keep the mechanical property of the matrix material. Because of the characteristics of the flame retardant, the flame retardant has been widely applied to the engineering plastic flame retardant fields of high processing temperature, high shear strength, high CTI value and the like, in particular to the fields of glass fiber reinforced nylon, polyester and the like.
In the commercialization field of organic phosphinate flame retardant, diethyl phosphinate aluminum, an OP series flame retardant of Clariant company, is the most successful, and related molecular structures and preparation methods are disclosed in series of patents.
According to the patent document published by Clariant company, the synthesis of the organic aluminum phosphinate flame retardant is generally accomplished in two steps: (1) Carrying out addition reaction on water-soluble inorganic hypophosphite and olefin in a water-phase medium, so that the inorganic hypophosphite is alkylated to obtain water-soluble alkylated hypophosphite; (2) The water-soluble alkylated hypophosphite and the water-soluble aluminum salt are subjected to double decomposition reaction to obtain organic aluminum hypophosphite precipitate, and the precipitate has high hydrophobicity and good flame retardant function. According to its synthetic mechanism, an organic aluminum phosphinate flame retardant is obtained by introducing an alkyl group into the molecular structure by addition of an inorganic hypophosphite to an olefin, and thus usually only dialkylphosphinates having the same alkyl group, such as commercially successfully used aluminum diethylphosphinate, are obtained, having the following molecular structure.
But for aluminum dialkylphosphinates with different alkyl groups, the molecular structure is as follows:
wherein R is 1 And R is 2 Are different and are all alkyl groups with carbon number not less than 2. For example, if ethyl propyl phosphinate aluminum, ethyl butyl phosphinate aluminum and the like are synthesized, two kinds of olefins are needed to be used for respectively mixing with phosphinesAcid addition, if a mixture containing a plurality of kinds of aluminum dialkylphosphinates is obtained according to the aforementioned production method, it is difficult to obtain aluminum dialkylphosphinates having different alkyl groups in high purity, and at the same time, since aluminum sulfate having an acid property is used in the second step of synthesizing an aluminum salt, aluminum sulfate remains in the product, so that the product exhibits acidity and is corrosive.
No report has been made concerning the preparation of aluminum dialkylphosphinates with different alkyl groups, particularly high purity products, and therefore, there is a need to develop a new synthetic process for aluminum dialkylphosphinates with different alkyl groups to prepare aluminum dialkylphosphinates with different alkyl groups in high purity.
According to the principle of addition reaction of olefin and inorganic hypophosphite and the characteristics of industrial production, a novel synthesis process is developed, and the purpose of the application is to prepare high-purity dialkyl aluminum phosphinate with different alkyl groups, so that the problem that the high-purity dialkyl aluminum phosphinate with different alkyl groups is difficult to obtain by the existing synthesis process is solved.
Disclosure of Invention
The main purpose of the application is to prepare high-purity dialkyl phosphinate aluminum with different alkyl groups, overcome the defect of low purity of the existing synthesis process, and the newly developed process utilizes the characteristics of stepwise addition reaction of olefin and low-concentration phosphinate aluminum solid in alkaline aqueous solution, water solubility of monoalkyl phosphinate aluminum and the like, and the purity of the prepared dialkyl phosphinate aluminum with different alkyl groups is more than 99.5%.
The dialkylphosphinic acid aluminum with different alkyl groups has the molecular structure shown as follows:
wherein R is 1 And R is 2 Are different and are all alkyl groups with carbon number not less than 2.
The specific technical scheme is as follows:
a method for preparing dialkylphosphinic acid aluminum with different alkyl groups, comprising the following steps:
(1) Dispersing aluminum hypophosphite solid in a solvent system containing alkali metal hydroxide and water in a low concentration, enabling olefin 1 and the aluminum hypophosphite solid to undergo an addition reaction at 100-150 ℃ and 0.1-0.3 MPa under the initiation of a free radical initiator, controlling the consumption of the olefin 1 until the aluminum hypophosphite solid fully reacts, preparing a monoalkyl aluminum phosphinate solution, filtering a precipitate, and collecting filtrate;
(2) Continuously introducing olefin 2 different from olefin 1 into the filtrate, and enabling the aluminum monoalkylphosphinate and olefin 2 to undergo an addition reaction at 100-150 ℃ and 0.1-0.3 MPa under the initiation of a free radical initiator to obtain aluminum dialkylphosphinate precipitates with different alkyl groups.
The present application will be described in detail below.
The present application aims at solving the problem that the existing technology is difficult to prepare high-purity dialkyl phosphinate aluminum with different alkyl groups, and the inventor has conducted extensive and intensive research. Aiming at the defects of the existing synthesis technology, the mechanism of the addition reaction of olefin and inorganic hypophosphite is intensively studied, and the result shows that:
1) The reaction of the olefin with two P-H bonds on the hypophosphite is carried out stepwise, and after the first P-H bond reacts with the olefin, the reactivity of the other P-H bond is reduced, i.e. the reaction of the olefin with the hypophosphite is carried out in two steps, namely the following two steps are carried out:
wherein R is H or alkyl.
It has been found that the reaction activity of the previous step is higher, usually the monoalkylphosphinate is first produced and the dialkylphosphinate is only started after the inorganic phosphinate has been converted to monoalkylphosphinate. Of course, there is a problem in that the initiation reaction is also likely to occur, and a small amount of monoalkylphosphinate is initiated to add to the olefin to form dialkylphosphinate before the inorganic phosphinate is completely converted into monoalkylphosphinate, and particularly under the condition of gas-liquid homogeneous reaction, the olefin and the Initiator (Initiator) can fully contact the monoalkylphosphinate to form dialkylphosphinate, so that the reaction rate is higher. Here only one olefin is used, and aluminum dialkylphosphinate with two identical alkyl groups is obtained.
2) Preparation of aluminum dialkylphosphinate with two different alkyl groups: if dialkylphosphinates with two different alkyl groups are to be prepared, two olefins are to be used. There are two schemes for using two olefins (olefin 1 and olefin 2):
(I) Olefin 1 (denoted R' 1 ) And olefin 2 (denoted R' 2 ) Simultaneously adding the reaction system, 3 reactions can simultaneously occur, and the reaction formula is shown as follows:
the resulting product comprises a product having two identical R' s 1 Dialkyl phosphinates of alkyl groups, with two identical R 2 Dialkyl phosphinates of alkyl groups and R with two different alkyl groups 1 And R is 2 Is a dialkylphosphinate salt of (2). Moreover, since the reaction rates of two olefins are different, it is common to obtain dialkylphosphinates of the kind having a high reaction rate, the ratio of the obtained dialkylphosphinates having two different alkyl groups is not high, these soluble dialkylphosphinates are all water-soluble, and aluminum dialkylphosphinate obtained after the reaction with an aluminum-containing compound is not water-soluble, and thus it is difficult to separate different kinds of aluminum dialkylphosphinates, and this scheme is difficult to obtain dialkylphosphinates having two different alkyl groups in high purity.
(II) staged addition of different olefins R' 1 And R'. 2 According to the foregoing description, the reaction of an olefin with two P-H bonds on the phosphinate is stepwise addition, but due to the use of soluble phosphinate, the resulting monoalkylphosphinate is also soluble, in which case a portion of the monoalkylphosphinate still is initiated and reacted with the olefin to give dialkylphosphinate with two identical alkyl groups, although this schemeThe higher purity of dialkylphosphinates with different alkyl groups than the previous solution in which two olefins were added simultaneously, however, these dialkylphosphinates with the same alkyl groups are difficult to separate from the mixture and thus high purity aluminum dialkylphosphinate still cannot be obtained.
In summary, it is difficult to prepare high purity aluminum dialkylphosphinates with different alkyl groups by prior methods.
Based on the previous results of the study, the inventors have surprisingly found that dispersing a non-water soluble inorganic aluminum hypophosphite in water still causes an addition reaction in the presence of an initiator and an olefin, which is similar to the conventional preparation process in that a non-water soluble aluminum hypophosphite and a water soluble hypophosphite are used, the addition reaction being similar. However, unlike conventional addition processes, this finding is different from the conventional addition process in that a water-soluble hypophosphite is used, which is dissolved in water to form a homogeneous system, a gas-liquid reaction occurs, and a non-water-soluble aluminum hypophosphite is used, which is dispersed in an aqueous phase to be in a suspended state, and the gas-liquid-solid reaction occurs here. Moreover, experiments also find that the generated aluminum monoalkylphosphinate is water-soluble, i.e. in the addition process, the non-water-soluble inorganic aluminum hypophosphite suspension gradually reduces or even completely disappears as the addition progresses, so that a homogeneous aqueous solution is obtained. If the addition reaction continues, a non-water-soluble dialkylphosphinic aluminum is formed and new precipitates are formed. Thus an olefin R 'can be used' 1 Is added to aluminum hypophosphite to form soluble monoalkyl (R 1 ) Aluminum phosphinate, during which there is still a chance of formation of part R 1 Aluminum dialkylphosphinate of (C), but R 1 The aluminum dialkylphosphinate of (2) is precipitated and thus can be used in the addition of another olefin R' 2 Before the reaction system is filtered, the obtained filtrate is high-purity monoalkyl (R 1 ) An aluminum phosphinate solution, in which case a second olefin R 'is added' 2 Let R 1 Aluminum monoalkylphosphinates and olefins R' 2 An addition reaction occurs, and R with different alkyl groups is generated 1 And R is 2 The aluminum dialkylphosphinate precipitates and has high purity. However, in this process, tooGenerating a certain proportion R' 1 And R'. 2 In order to further improve the purity, the inventor further researches and discovers that in the process of dispersing aluminum hypophosphite in an alkaline aqueous solution at low concentration and generating addition reaction under low olefin pressure, and combining a certain technological process, the content of the byproducts can be greatly reduced to obtain the higher-purity aluminum dialkylphosphinate with different alkyl groups.
In one embodiment, in step (1), the method for preparing the aluminum hypophosphite solid comprises: dissolving hypophosphorous acid and/or soluble hypophosphite in water, reacting with an aluminum-containing compound to prepare aluminum hypophosphite precipitate, and filtering and washing to obtain the aluminum hypophosphite solid.
In the method for preparing the aluminum hypophosphite solid, the soluble hypophosphite may be an alkali metal salt such as sodium hypophosphite, potassium hypophosphite, and the like.
In the preparation method of the aluminum hypophosphite solid, the aluminum-containing compound can be at least one of aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum hydroxide and aluminum acetate.
In the preparation method of the aluminum hypophosphite solid, if soluble hypophosphite is used, the aluminum salt compound can be selectively reacted; if hypophosphorous acid is used, it is optionally reacted with aluminum hydroxide.
In the preparation method of the aluminum hypophosphite solid, the washing can be carried out for a plurality of times by adopting clear water, so that the residue of hypophosphite or hypophosphorous acid is reduced, and the influence on subsequent reactions is reduced.
In the preparation method of the aluminum hypophosphite solid, the reaction temperature can be 20-120 ℃, and the reaction pressure can be 0.01-10 MPa.
In the step (1) and the step (2), the radical initiator may be a peroxide and/or an azo compound, preferably a water-soluble peroxide, and further preferably includes at least one of hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate.
The greater the number of carbons in the olefin, the lower the reactivity, and the second P-H bond activity decreases as the first is added to the olefin, so preferably, the application can be used to first remove the lower activity olefin (the higher carbon olefin) for the reaction with the second P-H bond, with faster reaction rates and higher conversions. In a preferred embodiment, the process for the preparation of aluminum dialkylphosphinate with different alkyl groups according to the present application, olefin 1 has a carbon number greater than olefin 2. Illustratively, olefin 1 is propylene or isobutylene, olefin 2 is ethylene, and the corresponding aluminum dialkylphosphinate with different alkyl groups obtained is aluminum ethylpropyl phosphinate or aluminum ethylbutyl phosphinate.
In step (1), the mass ratio of aluminum hypophosphite solids to water is 1:20-1000, and it has been found that too high an aluminum hypophosphite concentration will result in an increase in overadded byproducts.
Preferably, in the step (2), the mass percentage of the monoalkylaluminum phosphinate in the filtrate is not more than 5%. Too high a concentration of aluminum monoalkylphosphinate in the filtrate will result in an increase in overaddition by-products.
In the step (1), the olefin 1 and the aluminum hypophosphite solid are subjected to addition reaction at the temperature of 100-150 ℃ and the pressure of 0.1-0.3 MPa; in the step (2), the aluminum monoalkylphosphinate and the olefin 2 are subjected to addition reaction at 100-150 ℃ and 0.1-0.3 MPa under the initiation of a free radical initiator. Below 100 ℃, the reaction hardly proceeds; too high a pressure may lead to an increase in byproducts.
In one embodiment, the molar ratio of olefin 1 to aluminum hypophosphite solids in step (1) is from 0.1 to 3:1. The reaction degree is controlled according to the consumption amount of olefin, and according to the reaction formula, complete reaction occurs, the molar ratio of olefin 1 to aluminum hypophosphite is 3:1, and below this ratio, aluminum hypophosphite cannot be reacted completely, the conversion rate of aluminum hypophosphite is reduced, but the reduction of the content of byproducts is advantageous.
In one embodiment, the molar ratio of olefin 2 to aluminum monoalkylphosphinate in step (2) is from 0.1 to 3:1. According to the formula, a complete reaction takes place, the molar ratio of olefin 2 to the aluminum monoalkylphosphinate being 3:1, below which the aluminum monoalkylphosphinate cannot be reacted, the conversion of the aluminum monoalkylphosphinate being reduced but being advantageous for reducing the content of by-products.
Step (1) and step (2) are required to be carried out under alkaline conditions, and although the reaction may be carried out under acidic or neutral conditions, the amount of the excessive addition by-products obtained under acidic or neutral conditions may be increased. The required alkaline conditions are provided by alkali metal hydroxides. In step (1), the alkali metal hydroxide may be sodium hydroxide and/or potassium hydroxide, etc. In the step (1), the mass ratio of the alkali metal hydroxide to the water may be 1:50-10000.
After the reaction of the step (1) is completed, filtering is needed to filter the unreacted complete aluminum hypophosphite, the excessive addition by-product and a small amount of generated R 1 The filtrate was collected for the reaction of step (2). The absence of filtration results in increased byproducts.
In one embodiment, after the aluminum dialkylphosphinate precipitate obtained in step (2) is precipitated with different alkyl groups, the precipitate is further subjected to a filtration washing operation to isolate a product containing R 1 And R is 2 The precipitate can be washed with water to reduce R remained in the product 1 Aluminum monoalkylphosphinate of (a).
In one embodiment, the method for preparing the dialkyl aluminum phosphinate with different alkyl groups comprises the following steps:
s1, dissolving hypophosphorous acid and/or soluble hypophosphite in water, reacting with an aluminum-containing compound to prepare aluminum hypophosphite precipitate, filtering and washing the precipitate to obtain aluminum hypophosphite solid, wherein the reaction formula is as follows:
s2, dispersing the aluminum hypophosphite solid obtained in the step S1 in a solvent system containing alkali metal hydroxide and water in a low concentration, wherein the mass ratio of the aluminum hypophosphite solid to the water is 1:20-1000, and initiating the olefin R 'by a free radical initiator' 1 Carrying out addition reaction with aluminum hypophosphite solid at 100-150 ℃ and 0.1-0.3 MPa according to olefin R' 1 The consumption is controlled to react to the extent that the aluminum hypophosphite solid fully reacts to prepareTo monoalkyl (R) 1 ) Filtering the aluminum phosphinate solution, filtering the precipitate, and collecting filtrate; the reaction formula is as follows:
s3, continuously adding a second kind of olefin R 'into the filtrate collected in the step S2' 1 Different olefins R' 2 So that the mono alkyl (R 1 ) Aluminum phosphinate and olefins R' 2 Under the initiation of free radical initiator, the addition reaction is carried out at 100-150 ℃ and 0.1-0.3 MPa to obtain the product with different alkyl groups (R) 1 And R is 2 ) The dialkyl phosphinate aluminum precipitate is filtered and washed; the reaction formula is as follows:
the purity of the dialkyl phosphinate aluminum with different alkyl groups prepared by the preparation method of the dialkyl phosphinate aluminum with different alkyl groups is more than 99.5 percent.
Compared with the prior art, the application has the beneficial effects that:
the final step of the aluminum dialkylphosphinate with different alkyl groups is an addition reaction, and the reaction medium is in a weak alkaline condition, so that the acidic aluminum sulfate in the final precipitation step in the existing preparation method does not exist, and the product has lower acid residue, weaker acid and lower corrosiveness.
The dialkyl aluminum phosphinate with different alkyl groups prepared by the application can be used as a flame retardant in materials such as polyester, nylon, thermoplastic elastomer (TPE), polyurethane, epoxy resin, POK and the like.
The novel process for preparing the dialkyl aluminum phosphinate with different alkyl groups overcomes the defects of the prior synthesis process, and the raw material aluminum phosphinate and the intermediate byproducts are water-insoluble precipitates and can be quickly and simply separated from a target intermediate product solution without influencing the subsequent reaction and the purity of a final product, and the target intermediate product solution is only required to be taken for the second-step olefin addition reaction, so that the dialkyl aluminum phosphinate with different alkyl groups with higher purity can be obtained, and the process has more excellent performance.
Detailed Description
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application.
EXAMPLE 1 preparation of aluminum ethylpropyl phosphinate
Step one: 264g of sodium hypophosphite is dissolved in 1600g of water, the solution is transferred to a 3L reaction kettle, the temperature is raised to 80 ℃, 371.7g of aluminum sulfate solution with the concentration of 46wt% is added into the reaction kettle within 60min, white precipitate is gradually separated out, the reaction is completed, and the precipitate is filtered and washed by hot water to obtain the aluminum hypophosphite precipitate.
Step two: 2000g of water is added into a 3L pressure vessel, 74g of the aluminum hypophosphite precipitate prepared in the prior art is dispersed into the water, 1g of sodium hydroxide is added, the mixture is stirred uniformly, the temperature is raised to 110 ℃, propylene is introduced, the pressure in the reaction kettle is controlled to be constant at 0.3MPa, then a peristaltic pump is used for continuously pumping sodium persulfate solution with the concentration of 2wt%, the propylene consumption is measured, the propylene consumption is 42.3g, and the reaction time is about 2.5 hr. The reactor is depressurized and cooled to about 90 ℃, filtered and the filtrate is collected.
Step three: adding the filtrate into the pressure vessel, heating to 105 ℃, introducing ethylene, controlling the pressure in the reaction kettle to be constant at 0.3MPa, continuously pumping sodium persulfate solution with the concentration of 2wt% by using a peristaltic pump, metering the consumption of ethylene, stopping the reaction when the consumption of ethylene is not more, and controlling the reaction time to be about 3.0hr and the consumption of ethylene to be 28.7g. The reactor was depressurized and cooled to about 90 ℃, filtered, and the precipitate was washed with hot water and dried under vacuum at 130 ℃. The precipitate was subjected to phosphorus spectrum nuclear magnetic analysis, the composition of which is shown in table 1. 10g of the precipitate was dispersed in 100g of water, stirred well, left to stand for 1hr, and the pH of the solution was measured, and the results are shown in Table 1.
Table 1: sediment component analysis and pH test results
| Component (A) | Example 1 | Comparative example 1 |
| Ethylpropyl aluminum phosphinate (mol%) | 99.88 | 77.98 |
| Dipropylphosphinic acid aluminum (mol%) | 0.05 | 20.20 |
| Diethyl aluminum phosphinate (mol%) | 0.02 | 1.32 |
| Others (mol%) | 0.05 | 0.50 |
| pH | 5.1 | 4.0 |
Comparative example 1
The existing technology is adopted, soluble hypophosphite is added with olefin to obtain soluble dialkyl phosphinate, and then the soluble dialkyl phosphinate reacts with aluminum sulfate to obtain dialkyl phosphinate aluminum. The method comprises the following reaction steps:
step one: 264g of sodium hypophosphite is dissolved in 1600g of water, the solution is transferred to a 3L reaction kettle, 2g of sodium hydroxide is added, stirring is uniform, the temperature is raised to 110 ℃, propylene is introduced, the pressure in the reaction kettle is controlled to be constant at 0.3MPa, then a peristaltic pump is used for continuously pumping sodium persulfate solution with the concentration of 2wt%, the propylene consumption is measured, about 126.7g of propylene is consumed, propylene is stopped being introduced, ethylene is introduced again until the ethylene is not consumed any more, the reaction is finished, and the reaction time is 5.5hr.
Step two: the reaction solution obtained in the first step was heated to 95℃and 420g of an aluminum sulfate solution having a concentration of 46% by weight was added to the reaction vessel over 60 minutes, a white precipitate was gradually precipitated, and the reaction was completed, filtered, and the precipitate was washed with hot water and dried under vacuum at 130 ℃. The precipitate was subjected to phosphorus spectrometry nuclear magnetic analysis and pH test, and the results are shown in table 1.
EXAMPLE 2 Synthesis of aluminum ethylbutylphosphinate
The procedure was carried out in the same manner as in example 1 except that propylene in the second step was changed to isobutylene, and the consumption of isobutylene was 56.7g. The precipitate was subjected to phosphorus spectrometry nuclear magnetic analysis and pH test, and the results are shown in table 2.
Example 3
The procedure was carried out in the same manner as in example 2 except that the amount of aluminum hypophosphite precipitate in the second step was 55.5g. The precipitate was subjected to phosphorus spectrometry nuclear magnetic analysis and pH test, and the results are shown in table 2.
Example 4
The procedure was the same as in example 2, except that the reaction pressure in the second and third steps was 0.2MPa. The precipitate was subjected to phosphorus spectrometry nuclear magnetic analysis and pH test, and the results are shown in table 2.
Comparative example 2
The procedure was carried out in the same manner as in comparative example 1 except that propylene in the first step was changed to isobutylene, and the isobutylene consumption was 168.8g. The precipitate was subjected to phosphorus spectrometry nuclear magnetic analysis and pH test, and the results are shown in table 2.
Table 2: sediment component analysis and pH test results
| Component (A) | Example 2 | Comparative example 2 | Example 3 | Example 4 |
| Aluminum ethylbutyl phosphinate (mol%) | 99.87 | 76.07 | 99.89 | 99.91 |
| Dibutyl aluminum phosphinate (mol%) | 0.06 | 22.35 | 0.05 | 0.04 |
| Diethyl aluminum phosphinate (mol%) | 0.02 | 1.08 | 0.02 | 0.02 |
| Others (mol%) | 0.05 | 0.5 | 0.04 | 0.03 |
| pH | 5.0 | 3.9 | 5.0 | 5.0 |
Comparative example 3
The procedure was followed in the same manner as in example 2, except that in step two, 259g of aluminum hypophosphite was used. The precipitate product in the third step was subjected to phosphorus spectrum nuclear magnetic analysis, and the results thereof are shown in table 3.
Comparative example 4
The procedure was the same as in example 2, except that the reaction pressure in the second and third steps was 1.0MPa. The precipitation product in the third step was subjected to phosphorus spectrum nuclear magnetic analysis, and the results are shown in Table 3.
Comparative example 5
The procedure was as in example 2, except that sodium hydroxide was not used in step two. The precipitation product in the third step was subjected to phosphorus spectrum nuclear magnetic analysis, and the results are shown in Table 3.
Comparative example 6
The procedure was followed in the same manner as in example 2, except that sodium hydroxide was not used in the second step, and 3g of 98% by weight concentrated sulfuric acid was added. The precipitation product in the third step was subjected to phosphorus spectrum nuclear magnetic analysis, and the results are shown in Table 3.
Comparative example 7
The procedure was as in example 2, except that no filtration was performed in step two. The precipitation product in the third step was subjected to phosphorus spectrum nuclear magnetic analysis, and the results are shown in Table 3.
Comparative example 8
The procedure was the same as in example 2, except that the reaction temperature in the second step was 90 ℃. The reaction rate hardly proceeds.
Table 3: results of analysis of precipitate Components
Further, it is to be understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above description of the application, and that such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (10)
1. A method for preparing dialkylphosphinic acid aluminum with different alkyl groups, which is characterized by comprising the following steps:
(1) Dispersing aluminum hypophosphite solid in a solvent system containing alkali metal hydroxide and water in a low concentration, enabling olefin 1 and the aluminum hypophosphite solid to undergo an addition reaction at 100-150 ℃ and 0.1-0.3 MPa under the initiation of a free radical initiator, controlling the consumption of the olefin 1 until the aluminum hypophosphite solid fully reacts, preparing a monoalkyl aluminum phosphinate solution, filtering a precipitate, and collecting filtrate;
(2) Continuously introducing olefin 2 different from olefin 1 into the filtrate, and enabling the aluminum monoalkylphosphinate and olefin 2 to undergo an addition reaction at 100-150 ℃ and 0.1-0.3 MPa under the initiation of a free radical initiator to obtain aluminum dialkylphosphinate precipitates with different alkyl groups.
2. The method of claim 1, wherein in step (1), the method of preparing aluminum hypophosphite solids comprises: dissolving hypophosphorous acid and/or soluble hypophosphite in water, reacting with an aluminum-containing compound to prepare aluminum hypophosphite precipitate, and filtering and washing to obtain the aluminum hypophosphite solid.
3. The method according to claim 2, wherein the method for producing the aluminum hypophosphite solid comprises:
the soluble hypophosphite is an alkali metal salt;
the aluminum-containing compound is at least one of aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum hydroxide and aluminum acetate;
the temperature of the reaction is 20-120 ℃ and the pressure is 0.01-10 MPa.
4. The method according to claim 1, wherein in the step (1) and the step (2), the radical initiator is a peroxide and/or an azo compound, preferably a water-soluble peroxide, and further preferably at least one of hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate.
5. The process according to claim 1, wherein the olefin 1 has a carbon number greater than that of the olefin 2.
6. The method according to claim 1, wherein in the step (2), the content of the monoalkylaluminum phosphinate in the filtrate is not more than 5% by mass.
7. The process of claim 1 wherein the molar ratio of olefin 1 to aluminum hypophosphite solids in step (1) is from 0.1 to 3:1 and the molar ratio of olefin 2 to aluminum monoalkylphosphinate in step (2) is from 0.1 to 3:1.
8. The method according to claim 1, wherein in step (1):
the alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide;
the mass ratio of the alkali metal hydroxide to the water is 1:50-10000.
9. The process according to claim 1, wherein the precipitate is further subjected to a filtration washing operation after the precipitation of the aluminum dialkylphosphinate having a different alkyl group obtained in step (2).
10. The preparation method according to claim 1, wherein the purity of the aluminum dialkylphosphinate with different alkyl groups prepared by the preparation method is more than 99.5%.
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