CN107793448A - Alkyl phenyl tris phosphite of 3 hydroxyl 4 and preparation method thereof and the application as styrene analog thermoplastic elastomer age resistor - Google Patents
Alkyl phenyl tris phosphite of 3 hydroxyl 4 and preparation method thereof and the application as styrene analog thermoplastic elastomer age resistor Download PDFInfo
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000007983 Tris buffer Substances 0.000 title abstract 4
- 125000005037 alkyl phenyl group Chemical group 0.000 title abstract 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title abstract 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title abstract 4
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title abstract 3
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 53
- -1 2,4 dihydroxy phenyl Chemical group 0.000 claims abstract description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims abstract description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 14
- 150000005691 triesters Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 9
- 238000006856 Wolf-Kishner-Huang Minlon reduction reaction Methods 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 229920006978 SSBR Polymers 0.000 claims 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 abstract description 2
- 229960001755 resorcinol Drugs 0.000 abstract 2
- 230000032050 esterification Effects 0.000 abstract 1
- 230000032683 aging Effects 0.000 description 16
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 150000008301 phosphite esters Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- YVUZUKYBUMROPQ-UHFFFAOYSA-N mercury zinc Chemical compound [Zn].[Hg] YVUZUKYBUMROPQ-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 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
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
-
- 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
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- 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)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Application the invention discloses a kind of alkyl phenyl tris phosphite of 3 hydroxyl 4 and preparation method thereof and as styrene analog thermoplastic elastomer age resistor；The preparation method of the alkyl phenyl tris phosphite of 3 hydroxyl 4 is that resorcinol and monocarboxylic acid are carried out into friedel-crafts acylation, obtains 2,4 dihydroxy phenyl alkyl ketone compounds；2,4 dihydroxy phenyl alkyl ketone compounds obtain 4 alkyl-resorcin compounds by reducing carbonyl；The 4 alkyl-resorcin compound carries out esterification with phosphorus trichloride, produce, the alkyl phenyl tris phosphite of 3 hydroxyl 4 includes triphenyl phosphite structure and phenol type structure simultaneously, and a large amount of chain alkyls are introduced, there is the characteristics of resistance to volatilization, stability is good, can be used for styrene analog thermoplastic elastomer anti-aging, its dosage is few, significant effect, it is green, European Union's Reach laws and regulations requirements can be reached.
Description
Technical Field
The invention relates to a phosphite triester compound, a preparation method thereof and application of the phosphite triester compound as an anti-aging agent of a styrene thermoplastic elastomer, in particular to application of 3-hydroxy-4-alkylphenyl phosphite triester in the aspect of anti-aging of the styrene thermoplastic elastomer, belonging to the field of anti-aging of the styrene thermoplastic elastomer.
Background
The general styrene thermoplastic elastomer is a high molecular substance obtained by polymerizing styrene and butadiene (or isoprene) serving as monomers, cyclohexane or normal hexane serving as a solvent and alkyl lithium serving as an initiator through an anionic solution. The main common styrenic thermoplastic elastomers are: styrene-butadiene thermoplastic elastomer SBS and its hydrogenated product SEBS, pentylene thermoplastic elastomer SIS and its hydrogenated product SEPS and solution-polymerized styrene-butadiene rubber SSBR.
When the styrene thermoplastic elastomer is stored and used, an anti-aging agent needs to be added, and two anti-aging agents, namely a primary anti-aging agent and an auxiliary anti-aging agent, are generally added at present. The primary antioxidant is generally a hindered phenol, such as 2, 6-di-tert-butyl-p-cresol (264), and the formation of system radicals is generally prevented by active hydrogen atoms provided by the primary antioxidant itself. The auxiliary anti-aging agent is generally phosphite ester anti-aging agent, such as trinonyl phenyl phosphite (TNPP for short), the auxiliary anti-aging agent has the function of decomposing unstable hydrogen peroxide into stable compounds so as to avoid generating new free radicals, and the main anti-aging agent and the auxiliary anti-aging agent achieve the anti-aging effect of the styrene thermoplastic elastomer through the synergistic effect between the molecules of the two substances.
At present, an anti-aging system of a styrene thermoplastic elastomer is generally a 264 and TNPP system, the addition amount of 264 is 4-6 per mill (mass ratio), the addition amount of TNP is 4-6 per mill, the two are added together to account for about 10 per mill of the total amount of products, the addition amount is larger, 264 molecular weight, melting point (69-71 ℃) and flash point (126.7 ℃) are small, volatile and pollute the environment in the production, processing and use processes, the American and European Union have definitely forbidden the use in the styrene thermoplastic elastomer, the TNPP has definitely forbidden the use in the American and European Union because of containing nonylphenol, and the TNPP is forbidden by the European Reach project.
The anti-aging system of the styrene thermoplastic elastomer is generally compounded by a main anti-aging agent and an auxiliary anti-aging agent, has large addition amount, is easy to pollute the environment and damage human bodies, and has little addition amount, no environment pollution and no harm to human bodies for synthesizing the anti-aging agent through molecular design.
Disclosure of Invention
Aiming at the defects of the styrene thermoplastic elastic anti-aging agent in the prior art, the first purpose of the invention is to provide a 3-hydroxy-4-alkylphenyl phosphite triester compound which simultaneously contains a triphenyl phosphite structure and a phenol structure and introduces a large amount of long-chain alkyl, and the compound has the advantages of large molecular weight, volatilization resistance, good stability, environmental protection and capability of being used for anti-aging of styrene thermoplastic elastomers.
Another object of the present invention is to provide a method for preparing the 3-hydroxy-4-alkylphenyl phosphite triester, which is simple in operation, short in flow and low in cost.
The third purpose of the invention is to provide the application of the 3-hydroxy-4-alkyl phenyl phosphite triester as an anti-aging agent in the anti-aging of the styrene thermoplastic elastomer, and the anti-aging agent has the characteristics of volatilization resistance, small dosage, good stability and good anti-aging effect.
In order to achieve the above technical objects, the present invention provides a 3-hydroxy-4-alkylphenylphosphite triester having a structure of formula 1:
wherein,
R1、R2and R3Independently selected from C5～C20An alkyl group of (1).
The 3-hydroxy-4-alkyl phenyl phosphite triester has a special molecular structure, contains a hindered phenol structure and a phosphite ester structure, and introduces a large amount of long-chain alkyl. In the prior art, two compounds, namely sterically hindered phenol and phosphite ester, are compounded and combined and can be used as an anti-aging agent for a styrene thermoplastic elastomer. The 3-hydroxy-4-alkyl phenyl phosphite triester designed by the invention skillfully introduces a steric hindrance phenol structure and a phosphite ester structure at the same time, the two generate intramolecular synergistic effect, only one compound of the 3-hydroxy-4-alkyl phenyl phosphite triester is added, the anti-aging performance of the styrene thermoplastic elastomer can be better improved, and the usage amount of the anti-aging agent is greatly reduced. Meanwhile, the introduction of a large amount of long-chain alkyl increases the molecular weight of the anti-aging agent, can reduce the volatilization loss of products in the production and processing processes, improves the thermal stability, and avoids environmental pollution. And meanwhile, the steric hindrance around the phosphorus atom is increased, so that the hydrolysis stability of the product is improved, and the requirements of environmental protection, high efficiency and conservation are met.
Preferred embodiment, R in formula 11、R2And R3Are the same alkyl groups.
More preferably, R in formula 11、R2And R3Are identical linear alkyl radicals.
The invention also provides a method for preparing the 3-hydroxy-4-alkylphenyl phosphite triester, which comprises the following steps:
1) resorcinol with C5～C20The monocarboxylic acid is subjected to Friedel-crafts acylation reaction to obtain a2, 4-dihydroxy phenyl alkyl ketone compound;
2) the 2, 4-dihydroxyphenyl alkyl ketone compound is reduced by a Huang Minlon reduction method to obtain a 4-alkyl resorcinol compound;
3) and carrying out esterification reaction on the 4-alkyl resorcinol compound and phosphorus trichloride to obtain 3-hydroxy-4-alkyl phenyl phosphite triester.
In a preferred scheme, the Friedel-crafts acylation reaction conditions are as follows: and (3) reacting for 40-120min at the temperature of 20-80 ℃ by taking Lewis acid as a catalyst.
In a preferred scheme, the reaction conditions of the Huang Minlon reduction method are as follows: the reaction is carried out at 245-250 ℃ for 180-240 min.
In a preferred embodiment, the esterification reaction conditions are as follows: reacting for 60-120min at 20-60 ℃. Phosphorus trichloride is preferably added in portions or stepwise to the reaction system containing the 4-alkylresorcinol compound during the esterification reaction.
The invention also provides application of the 3-hydroxy-4-alkylphenyl phosphite triester, and the 3-hydroxy-4-alkylphenyl phosphite triester is applied to ageing prevention of a styrene thermoplastic elastomer as an anti-aging agent.
In a preferable embodiment, the addition amount of the 3-hydroxy-4-alkyl phenyl phosphite triester in the styrene thermoplastic elastomer is less than or equal to 3 wt%.
More preferably, the styrene-based thermoplastic elastomer includes at least one of styrene-butadiene thermoplastic elastomer SBS (block copolymer of butadiene styrene), SEBS hydrogenated SBS, SSBR (solution polymerized styrene-butadiene rubber), SIS (pentylene thermoplastic elastomer), and SEPS (hydrogenated SIS).
The preparation method of the 3-hydroxy-4-alkyl phenyl phosphite triester comprises the following steps:
1) resorcinol with C5～C20Long-chain fatty acid is subjected to Friedel-crafts reaction under the action of a Lewis acid catalyst;
2) the 2, 4-dihydroxyphenyl alkyl ketone compound is reduced by using Huang Minlon to selectively reduce carbonyl into methylene;
3) gradually adding phosphorus trichloride into a system containing a 4-alkyl resorcinol compound (a mixed 4-alkyl resorcinol compound with different alkyl substituents can be adopted for reaction), and carrying out esterification reaction to obtain a target product;
compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the 3-hydroxy-4-alkyl phenyl phosphite triester compound simultaneously contains main structural units of a hindered phenol main anti-aging agent and a phosphite ester auxiliary anti-aging agent, and the advantages of intramolecular synergy generated by the two structural units are obviously superior to intermolecular synergy when the traditional hindered phenol main anti-aging agent and the phosphite ester auxiliary anti-aging agent are used in combination. The 3-hydroxy-4-alkyl phenyl phosphite triester compound can realize the anti-aging of the styrene thermoplastic elastomer.
The 3-hydroxy-4-alkyl phenyl phosphite triester compound introduces a large amount of long-chain alkyl, the long-chain alkyl enables the molecular weight of the 3-hydroxy-4-alkyl phenyl phosphite triester to be increased, the volatility resistance is enhanced, the volatilization loss of products in the production and processing processes can be reduced, and the thermal stability is strong. On the other hand, the steric hindrance around the phosphorus atom is increased, the hydrolysis stability of the product is improved, the requirements of green, environmental protection, high efficiency and saving are met, and the requirement of the European Union Reach act is met.
The 3-hydroxy-4-alkyl phenyl phosphite triester compound has the advantages of small addition amount in the styrene thermoplastic elastomer, obvious effect, reduction of the use amount of the anti-aging agent and reduction of the use cost.
The preparation method of the 3-hydroxy-4-alkyl phenyl phosphite triester compound is simple, short in flow, high in yield and capable of meeting the requirements of large-scale production.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
350g of metered resorcinol and carboxylic acid (refer to table 1) with different carbon atoms and 10g of zinc chloride are added into a reaction kettle, the reaction temperature is controlled within 20-80 ℃, the reaction time is controlled within 40-120min, and samples A1, B1, C1, D1, E1 and F1 are respectively obtained after treatment.
TABLE 1
| Serial number | Carboxylic acids of different carbon atoms | Quality (g) | Sample number |
| A | Valeric acid | 530 | A1 |
| B | Hexanoic acid | 563 | B1 |
| C | Heptanoic acid | 607 | C1 |
| D | Octanoic acid | 645 | D1 |
| E | Pelargonic acid | 690 | E1 |
| F | Capric acid | 714 | F1 |
By using samples A1-F1 in Table 1, adding a zinc-mercury reagent and a solvent into a reaction kettle, controlling the reaction temperature at 245-:
TABLE 2
Samples A21-F21 in Table 2 were used, 15-25g of phosphorus trichloride was added to a reaction kettle, the reaction temperature was controlled at 20-60 ℃ and the reaction time was controlled at 60-120min, and samples A31-F31 were obtained, respectively, as shown in Table 3:
TABLE 3
| Sample number | Addition amount (g) | Sample number |
| A2-1 | 250 | A3-1 |
| B2-1 | 250 | B3-1 |
| C2-1 | 250 | C3-1 |
| D2-1 | 250 | D3-1 |
| E2-1 | 250 | E3-1 |
| F2-1 | 250 | F3-1 |
Aging evaluation tests are carried out on all prepared novel environment-friendly anti-aging agents A3-1, B3-1, C3-1, D3-1, E3-1 and F3-1, and a comparative high-temperature (70-75 ℃) hot air accelerated aging test is carried out on 5.0 per mill of anti-aging agent and 5 per mill of anti-aging agent and 264 and TNPP respectively by taking thermoplastic elastomer SBSYH-791h as an example, and the results are shown in tables 4-1-4-6:
TABLE 4-1A 3-1 vs. 264/TNP system aging
Under the condition of the same additive amount, the A3-1 sample has the same anti-aging effect in SBS as the existing 264/TNP complex system.
TABLE 4-2B 3-1 comparison with 264/TNP system aging
Under the condition of the same additive amount, the B3-1 sample has the same anti-aging effect in SBS as the prior 264/TNP complex system.
TABLE 4-3C 3-1 vs. 264/TNP system aging
Under the condition of the same additive amount, the anti-aging effect of the C3-1 sample in SBS is equivalent to that of the existing 264/TNP complex system.
TABLE 4-4D 3-1 vs. 264/TNP system aging
Under the condition of the same additive amount, the anti-aging effect of the D3-1 sample in SBS is equivalent to that of the existing 264/TNP complex system.
TABLE 4-5E 3-1 comparison to 264/TNP system aging
Under the condition of the same additive amount, the E3-1 sample has the same anti-aging effect in SBS as the existing 264/TNP complex system.
TABLE 4-6F 3-1 vs. 264/TNP system aging
Under the condition of the same additive amount, the F3-1 sample has the same anti-aging effect in SBS as the prior 264/TNP complex system.
E3-1 is selected to explain different addition amounts in comparison, the accelerated aging speed is measured by hot air at the high temperature of 70-75 ℃, the accelerated aging time is 120H by taking SBSYH-791H as an example, and the result is shown in Table 5:
TABLE 5 aging results for different loadings of E3-1
As can be seen from the above tests, when the addition amount of the novel anti-aging agent is more than 2.5 per mill, the anti-aging effect of the novel anti-aging agent is equivalent to that of 264/TNP with 5 per mill.
The novel anti-aging agent A3-2-F3-2 prepared by the invention is popularized to SIS, the addition amount is 3 per mill, the aging time is 120h in a hot air accelerated aging experiment at 70-75 ℃, and the results are shown in Table 6:
TABLE 6 SISYH-1105 Hot air acceleration example
In this embodiment, when the sample of the present invention is added in an amount of 3%, the anti-aging effect in SIS can completely reach 5% corresponding to that of 264 and TNPP composite system.
Samples A3-1, B3-1, C3-1, D3-1, E3-1 and F3-1 prepared by the method are popularized to solution polymerized butylbenzene YH-2601, the addition amount is 3 per mill, the aging time is 120h in a hot air high-temperature accelerated aging test at 70-75 ℃, and the implementation results are shown in Table 7:
TABLE 7
And (3) product structure characterization:
31PNMR:-19.9(S),
1HNMR:0.9-2.55(m,17H),5.0(s,3H),7.15(s,3H),6.94(d,J＝7.0,3H),7.24(d,J＝7.0,3H).
13CNMR:14.0,23.1,32.5,30,30.3,29.9,32.7,25.6,102,108.1 119.5,131,155.3,158.4。
Claims (10)
- 3-hydroxy-4-alkylphenyl phosphite triester characterized by: has the structure of formula 1:wherein,R1、R2and R3Independently selected from C5～C20An alkyl group of (1).
- 2. 3-hydroxy-4-alkylphenyl phosphite triester as claimed in claim 1, characterized in that: r1、R2And R3Are the same alkyl groups.
- 3. 3-hydroxy-4-alkylphenyl phosphite triester as claimed in claim 1 or 2, characterized in that: r1、R2And R3Are the same straight alkyl radicals.
- 4. A process for preparing a 3-hydroxy-4-alkylphenyl phosphite triester as claimed in any one of claims 1 to 3, characterized in that: the method comprises the following steps:1) resorcinol with C5～C20The monocarboxylic acid is subjected to Friedel-crafts acylation reaction to obtain a2, 4-dihydroxy phenyl alkyl ketone compound;2) the 2, 4-dihydroxyphenyl alkyl ketone compound is reduced by a Huang Minlon reduction method to obtain a 4-alkyl resorcinol compound;3) and carrying out esterification reaction on the 4-alkyl resorcinol compound and phosphorus trichloride to obtain 3-hydroxy-4-alkyl phenyl phosphite triester.
- 5. The method of claim 4 for preparing 3-hydroxy-4-alkylphenyl phosphite triester, wherein: the conditions of the Friedel-crafts acylation reaction are as follows: and (3) reacting for 40-120min at the temperature of 20-80 ℃ by taking Lewis acid as a catalyst.
- 6. The method of claim 4 for preparing 3-hydroxy-4-alkylphenyl phosphite triester, wherein: the reaction conditions of the Huang Minlon reduction method are as follows: the reaction is carried out at 245-250 ℃ for 180-240 min.
- 7. The method of claim 4 for preparing 3-hydroxy-4-alkylphenyl phosphite triester, wherein: the esterification reaction conditions are as follows: reacting for 60-120min at the temperature of 20-60 ℃.
- 8. Use of a 3-hydroxy-4-alkylphenyl phosphite triester as claimed in any one of claims 1 to 3, wherein: the 3-hydroxy-4-alkyl phenyl phosphite triester is used as an anti-aging agent for the styrene thermoplastic elastomer for anti-aging.
- 9. Use of a 3-hydroxy-4-alkylphenyl phosphite triester as claimed in claim 8, wherein: the addition amount of the 3-hydroxy-4-alkyl phenyl phosphite triester in the styrene thermoplastic elastomer is less than or equal to 3 wt%.
- 10. Use of a 3-hydroxy-4-alkylphenyl phosphite triester as claimed in claim 9, wherein: the styrene thermoplastic elastomer comprises at least one of styrene-butadiene thermoplastic elastomers SBS, SEBS, SSBR, SIS and SEPS.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4705879A (en) * | 1986-01-13 | 1987-11-10 | Koppers Company, Inc. | Long-chain alkylresorcinol phosphites |
| CN103159596A (en) * | 2011-12-14 | 2013-06-19 | 南京华狮化工有限公司 | Preparation method for 4-butylresorcinol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4705879A (en) * | 1986-01-13 | 1987-11-10 | Koppers Company, Inc. | Long-chain alkylresorcinol phosphites |
| CN103159596A (en) * | 2011-12-14 | 2013-06-19 | 南京华狮化工有限公司 | Preparation method for 4-butylresorcinol |
Non-Patent Citations (1)
| Title |
|---|
| 邢其毅 等编著: "《基础有机化学 （第三版）上册》", 30 June 2005, 北京：高等教育出版社 * |
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