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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- CN107793448A CN107793448A CN201610806283.8A CN201610806283A CN107793448A CN 107793448 A CN107793448 A CN 107793448A CN 201610806283 A CN201610806283 A CN 201610806283A CN 107793448 A CN107793448 A CN 107793448A
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- alkyl
- hydroxyl
- alkyl phenyl
- phenyl tris
- thermoplastic elastomer
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- 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 System
- 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
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 present invention relates to a kind of tris phosphite class compound and preparation method thereof and as styrene analog thermoplastic elasticity
The application of body age resistor, more particularly to 3- hydroxyls -4- alkyl phenyls tris phosphite are anti-old in styrene analog thermoplastic elastomer
Application in terms of change, belong to styrene analog thermoplastic elastomer anti-aging field.
Background technology
Conventional styrene analog thermoplastic elastomer refers to styrene, butadiene (or isoprene) for monomer, with ring
Hexane or n-hexane are solvent, using lithium alkylide as initiator, the polymer substance that is formed by anionic solution polymerization.Common
Styrene analog thermoplastic elastomer mainly has：Butylbenzene thermoplastic elastomer SBS and its hydrogenation product SEBS, penta benzene thermoplastic elastic
Body SIS and its hydrogenation product SEPS and solution polymerized butadiene styrene rubber SSBR.
Styrene analog thermoplastic elastomer is in storage and in use, needing to add age resistor, and general two kinds of addition is anti-at present
Old agent, i.e., main age resistor and auxiliary age resistor.Main age resistor is generally sterically hindered phenol, such as 2.6- toluene di-tert-butyl phenols (referred to as
264) formation of system free radical typically, is prevented by the reactive hydrogen atom of main age resistor itself offer.Aid in age resistor one
As be phosphite ester age resistor, such as trisnonylphenyl phosphite (abbreviation TNPP), the effect of auxiliary age resistor is will be unstable
Hydrogen peroxide resolves into stable compound in order to avoid producing new free radical, and main and auxiliary two kinds of age resistor pass through between two kinds of material molecules
Synergy reach the anti-aging effect of styrene analog thermoplastic elastomer.
At present, styrenic thermoplastic elastomer's antiaging system is generally 264 and TNPP systems, and addition 264 is 4-6 ‰
(mass ratio), TNP are 4-6 ‰, and both, which are added together, accounts for 10 ‰ of product population or so, and addition is larger, simultaneously because 264
Molecular weight is small, fusing point is low (69-71 DEG C), flash-point is low (126.7 DEG C), volatile during producing and processing use, pollutes ring
Border, the U.S., European Union clearly forbid it to be used in styrene analog thermoplastic elastomer, TNPP due to containing nonyl phenol to human body
There is harm, the U.S., European Union have also clearly prohibitted the use of, are forbidden by European Union's Reach bills.
The preventing aging system of above-mentioned styrene analog thermoplastic elastomer typically uses main and auxiliary two kinds of antiaging agent compounding uses,
Addition is big, easily pollutes environment, injury human body, and a kind of by the anti-old of intramolecular collaboration for being synthesized by MOLECULE DESIGN
Agent, addition is few, free from environmental pollution, and the age resistor for not injuring human body is also not directed to.
The content of the invention
The defects of existing for styrene analog thermoplastic elasticity age resistor of the prior art, of the invention first purpose
It is to be to provide one kind while include triphenyl phosphite structure and phenol type structure, and the 3- hydroxyls of a large amount of chain alkyls of introducing-
4- alkyl phenyl tris phosphite compounds, the compound molecular weight is big, and resistance to volatilization, stability are good, green, available for benzene
The anti-aging of ethene analog thermoplastic elastomer.
Another object of the present invention be to provide it is a kind of it is simple to operate, flow is short, cost it is low prepare the 3- hydroxyls
The method of base -4- alkyl phenyl tris phosphites.
Third object of the present invention is to be to provide the 3- hydroxyls -4- alkyl phenyl tris phosphites as age resistor
Application in styrene analog thermoplastic elastomer anti-aging, with resistance to volatilization, dosage is small, stability is good, and anti-aging effect is good
The characteristics of.
In order to realize above-mentioned technical purpose, the invention provides a kind of 3- hydroxyls -4- alkyl phenyl tris phosphites, and it has
There is the structure of formula 1：
Wherein,
R1、R2And R3Independently selected from C5~C20Alkyl.
3- hydroxyl -4- alkyl phenyl the tris phosphites of the present invention have special molecular structure, and it contains position simultaneously
Phenol and phosphite ester structure are hindered, and introduces substantial amounts of chain alkyl.In the prior art, two kinds of chemical combination of sterically hindered phenol and phosphite ester
Thing compounded combination, it can be used with styrene analog thermoplastic elastomer age resistor.And the 3- hydroxyl -4- alkyl phenyls that the present invention designs
Tris phosphite dexterously introduces sterically hindered phenol structure and phosphite ester structure simultaneously, and both produce the synergy of intramolecular,
A kind of compound of 3- hydroxyl -4- alkyl phenyl tris phosphites is only added, can preferably improve styrene analog thermoplastic elastomer
Anti ageing property, greatly reduce the usage amount of age resistor.Meanwhile the introducing of a large amount of chain alkyls, make the molecular weight of age resistor
Increase, it is possible to reduce product is producing the volatilization loss with process, improves heat endurance, avoids polluting environment.Phosphorus simultaneously
Steric hindrance increase around atom, the hydrolytic stability of product is improved, reaches green, environmental protection, the requirement of efficient economizing.
Preferable scheme, R in formula 11、R2And R3For identical alkyl.
More preferably scheme, R in formula 11、R2And R3For identical linear paraffin base.
Present invention also offers the method for preparing described 3- hydroxyl -4- alkyl phenyl tris phosphites, this method includes
Following steps：
1) resorcinol and C5~C20Monocarboxylic acid carries out friedel-crafts acylation, obtains 2,4- dihydroxy phenyl alkyl ketones
Compound；
2) 2, the 4- dihydroxy phenyls alkyl ketone compound is reduced using huang-Minlon reduction, obtains 4- alkyl resorsinols two
Phenolic compounds；
3) the 4- alkyl-resorcins compound carries out esterification with phosphorus trichloride, obtains 3- hydroxyl -4- alkylbenzenes
Base tris phosphite.
Preferable scheme, friedel-crafts acylation condition are：Using lewis acid as catalyst, in 20 DEG C~80 DEG C temperature
Under the conditions of react 40~120min.
Preferable scheme, the reaction condition of the huang-Minlon reduction are：Reaction is at a temperature of 245~250 DEG C, reaction
180~240min.
Preferable scheme, esterification condition are：60~120min is reacted at a temperature of 20~60 DEG C.Esterification reaction process
Middle phosphorus trichloride preferably adds or is added step-wise in the reaction system of the compound of alkyl-resorcin containing 4- in batches to react.
Present invention also offers the application of described 3- hydroxyl -4- alkyl phenyl tris phosphites, by the 3- hydroxyls -4-
Alkyl phenyl tris phosphite is applied to styrene analog thermoplastic elastomer anti-aging as age resistor.
Preferable scheme, the 3- hydroxyls -4- alkyl phenyl tris phosphites are in styrene analog thermoplastic elastomer
Addition≤3wt ‰.
More preferably scheme, described styrene analog thermoplastic elastomer include butylbenzene thermoplastic elastomer's SBS (butadiene
The block copolymer of styrene), SEBS Hydrogenated SBSs), SSBR (solution polymerized butadiene styrene rubber), SIS (penta benzene thermoplastic elastomer (TPE)),
At least one of SEPS (hydrogenation SIS).
The preparation method of the 3- hydroxyl -4- alkyl phenyl tris phosphites of the present invention, comprises the following steps：
1) resorcinol and C5~C20Long chain fatty acids, under lewis acid catalyst effect, carry out Friedel-Crafts reaction；
2) 2,4- dihydroxy phenyls alkyl ketone compound uses Huang Min-lon reduction, by carbonyl selective reduction into methylene；
3) phosphorus trichloride be added step-wise to the compound of alkyl-resorcin containing 4- (can use there are different alkyl substituents
Mixing 4- alkyl-resorcin compounds reacted) system in, carry out esterification, obtain target product；
Compared with the prior art, the advantageous effects that technical scheme is brought：
3- hydroxyl -4- alkyl phenyl tris phosphite the compounds of the present invention contain the main age resistor of sterically hindered phenol and Asia simultaneously
Phosphoric acid ester aids in the essential building blocks of age resistor, and intramolecular synergy is with the obvious advantage caused by two kinds of construction units is better than
Intermolecular synergy when the main age resistor of traditional sterically hindered phenol is applied in combination with phosphorous acid esters auxiliary age resistor.Use this hair
Styrene analog thermoplastic elastomer anti-aging can be achieved in bright 3- hydroxyl -4- alkyl phenyl tris phosphites compound.
3- hydroxyl -4- alkyl phenyl tris phosphite the compounds of the present invention introduce substantial amounts of chain alkyl, long alkane
Base increases the molecular weight of 3- hydroxyl -4- alkyl phenyl tris phosphites, volatility resistance enhancing, it is possible to reduce product production and
The volatilization loss of process, heat endurance are strong.On the other hand, the steric hindrance increase around phosphorus atoms, improves product
Hydrolytic stability, reach green, environmental protection, the requirement of efficient economizing, and meet European Union's Reach bills requirement.
3- hydroxyl -4- alkyl phenyl tris phosphite the compounds of the present invention are in styrene analog thermoplastic elastomer addition
It is few, significant effect, the usage amount of age resistor is reduced, reduces use cost.
3- hydroxyl -4- alkyl phenyl tris phosphite the compounds process for production thereof of the present invention is simple, and flow is short, high income,
Meet that large-scale production requires.
Embodiment
Following examples are intended to further illustrate present invention, rather than the protection model of limitation the claims in the present invention
Enclose.
Embodiment 1
The carboxylic acid (with reference to table 1) of the resorcinol 350g and different carbon atoms measured, zinc chloride are added in a kettle
10g, in 20 DEG C -80 DEG C of controlling reaction temperature, reaction time 40-120min, through processing respectively obtain sample A1, B1, C1, D1,
E1、F1。
Table 1
| Sequence number | Different carbon atom carboxylic acids | Quality (g) | Sample sequence number |
| A | Valeric acid | 530 | A1 |
| B | Caproic acid | 563 | B1 |
| C | Enanthic acid | 607 | C1 |
| D | Octanoic acid | 645 | D1 |
| E | N-nonanoic acid | 690 | E1 |
| F | Capric acid | 714 | F1 |
Using the sample A1-F1 of table 1, zinc-mercury reagent and solvent are added in a kettle, 245-250 DEG C of controlling reaction temperature,
Reaction time 180-240min, sample A21-F21 is respectively obtained, is shown in Table 2：
Table 2
Using the sample A21-F21 of table 2, phosphorus trichloride 15-25g is added in a kettle, 20-60 DEG C of controlling reaction temperature,
Reaction time 60-120min, sample A31-F31 is respectively obtained, is shown in Table 3：
Table 3
| Sample number | Addition (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 examination is carried out to novel environment friendly antioxidant A 3-1, B3-1, C3-1, D3-1, E3-1, F3-1 of all preparations
Test, by taking thermoplastic elastomer SBS YH-791h as an example, age resistor addition is 5.0 ‰ and 264 respectively to add 5 ‰ with TNPP and carry out pair
Than high temperature (70-75 DEG C) hot-air accelerated aging test, 4-1-4-6 the results are shown in Table：
Table 4-1 A3-1 contrast with the aging of 264/TNP systems
In the case of equal additive capacity, A3-1 samples and existing 264/TNP compound systems anti-aging effect in SBS
Quite.
Table 4-2 B3-1 contrast with the aging of 264/TNP systems
In the case of equal additive capacity, B3-1 samples and existing 264/TNP compound systems anti-aging effect in SBS
Quite.
Table 4-3 C3-1 contrast with the aging of 264/TNP systems
In the case of equal additive capacity, C3-1 samples and existing 264/TNP compound systems anti-aging effect in SBS
Quite.
Table 4-4 D3-1 contrast with the aging of 264/TNP systems
In the case of equal additive capacity, D3-1 samples and existing 264/TNP compound systems anti-aging effect in SBS
Quite.
Table 4-5 E3-1 contrast with the aging of 264/TNP systems
In the case of equal additive capacity, E3-1 samples and existing 264/TNP compound systems anti-aging effect in SBS
Quite.
Table 4-6 F3-1 contrast with the aging of 264/TNP systems
In the case of equal additive capacity, F3-1 samples and existing 264/TNP compound systems anti-aging effect in SBS
Quite.
Choose E3-1 contrasts and explain different additions, tested the speed in 70-75 DEG C of high-temperature hot air accelerated ageing, with SBSYH-
Exemplified by 791H, the accelerated ageing time is 120h, the results are shown in Table 5：
The ageing results of the E3-1 difference additions of table 5
Tested more than, new age resistor addition be more than 2.5 ‰ when, the anti-aging effect of new age resistor with
The anti-aging effect of 264/TNP additions 5 ‰ is suitable.
Prepared by the present invention into new antioxidant A 3-2-F3-2 to be generalized in SIS, addition is 3 ‰ empty in 70-75 DEG C of heat
Gas accelerated aging tests, ageing time 120h, the results are shown in Table 6：
The SISYH-1105 hot-airs of table 6 accelerate embodiment
In the present embodiment, inventive samples addition be 3 ‰ when, in SIS anti-aging effect fully achieve with
264th, TNPP compound systems are suitable to addition 5 ‰.
Sample A3-1, B3-1, C3-1, D3-1, E3-1, F3-1 prepared by the present invention are generalized to solution polymerized butylbenzene YH-2601
In, addition is 3 ‰, and in 70-75 DEG C of hot-air high temperature accelerated aging test, ageing time 120h, result of implementation is shown in Table
7：
Table 7
Product structure characterizes：
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)
1.3- hydroxyl -4- alkyl phenyl tris phosphites, it is characterised in that：With the structure of formula 1：
Wherein,
R1、R2And R3Independently selected from C5~C20Alkyl.
2. 3- hydroxyls -4- alkyl phenyl tris phosphites according to claim 1, it is characterised in that：R1、R2And R3For phase
Same alkyl.
3. 3- hydroxyls -4- alkyl phenyl tris phosphites according to claim 1 or 2, it is characterised in that：R1、R2And R3For
The direct-connected alkyl of identical.
4. preparing the method for the 3- hydroxyl -4- alkyl phenyl tris phosphites described in any one of claims 1 to 3, its feature exists
In：Comprise the following steps：
1) resorcinol and C5~C20Monocarboxylic acid carries out friedel-crafts acylation, obtains 2,4- dihydroxy phenyl alkyl ketone chemical combination
Thing；
2) 2, the 4- dihydroxy phenyls alkyl ketone compound is reduced using huang-Minlon reduction, obtains 4- alkyl-resorcins
Compound；
3) the 4- alkyl-resorcins compound carries out esterification with phosphorus trichloride, obtains 3- hydroxyl -4- alkyl phenyls Asia
Phosphotriester.
5. the method according to claim 4 for preparing 3- hydroxyl -4- alkyl phenyl tris phosphites, it is characterised in that：Institute
The condition for stating friedel-crafts acylation is：Using lewis acid as catalyst, under 20 DEG C~80 DEG C temperature conditionss, reaction 40~
120min。
6. the method according to claim 4 for preparing 3- hydroxyl -4- alkyl phenyl tris phosphites, it is characterised in that：Institute
The reaction condition for stating huang-Minlon reduction is：Reaction reacts 180~240min at a temperature of 245~250 DEG C.
7. the method according to claim 4 for preparing 3- hydroxyl -4- alkyl phenyl tris phosphites, it is characterised in that：Institute
The condition for stating esterification is：At a temperature of 20~60 DEG C, 60~120min is reacted.
8. the application of the 3- hydroxyl -4- alkyl phenyl tris phosphites described in any one of claims 1 to 3, it is characterised in that：Institute
State 3- hydroxyls -4- alkyl phenyls tris phosphite and be applied to styrene analog thermoplastic elastomer anti-aging as age resistor.
9. the application of 3- hydroxyls -4- alkyl phenyl tris phosphites according to claim 8, it is characterised in that：The 3-
Addition≤3wt ‰ of the hydroxyl -4- alkyl phenyl tris phosphites in styrene analog thermoplastic elastomer.
10. the application of 3- hydroxyls -4- alkyl phenyl tris phosphites according to claim 9, it is characterised in that：Described
Styrene analog thermoplastic elastomer includes at least one of butylbenzene thermoplastic elastomer SBS, SEBS, SSBR, SIS, SEPS.
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| CN201610806283.8A CN107793448B (en) | 2016-09-06 | 2016-09-06 | 3-hydroxy-4-alkyl phenyl phosphite triester, preparation method thereof and application thereof as styrene thermoplastic elastomer anti-aging agent |
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|---|---|---|---|
| CN201610806283.8A CN107793448B (en) | 2016-09-06 | 2016-09-06 | 3-hydroxy-4-alkyl phenyl phosphite triester, preparation method thereof and application thereof as styrene thermoplastic elastomer anti-aging agent |
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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 |
-
2016
- 2016-09-06 CN CN201610806283.8A patent/CN107793448B/en active Active
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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