CN107573373A - A kind of preparation method of liquid phosphite antioxidant - Google Patents

A kind of preparation method of liquid phosphite antioxidant Download PDF

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Publication number
CN107573373A
CN107573373A CN201710843377.7A CN201710843377A CN107573373A CN 107573373 A CN107573373 A CN 107573373A CN 201710843377 A CN201710843377 A CN 201710843377A CN 107573373 A CN107573373 A CN 107573373A
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reaction
butylamine
isooctanol
phosphite antioxidant
liquid phosphite
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CN201710843377.7A
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曹标
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Western Neil Chemical Industry Science Co Ltd Of Oil Of Spc
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Western Neil Chemical Industry Science Co Ltd Of Oil Of Spc
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Abstract

The invention provides a kind of preparation method of liquid phosphite antioxidant, comprise the following steps:Phosphorus trichloride, anacardol, isooctanol are added into reaction vessel, and adds the methyl tricapryl ammonium chloride as catalyst, gradient increased temperature reaction;Isooctanol is added, continues to react;After reaction completely, the complete isooctanol of unreacted is distilled out, is reclaimed;Di-n-butylamine, tri-n-butylamine are added into reaction vessel to carry out neutralization reaction, obtains product mixture;The complete di-n-butylamine of unreacted, tri-n-butylamine are distilled out, is reclaimed;Heat filtering, filtrate is taken, produce the liquid phosphite antioxidant.The preparation method process route is short, and reaction condition is gentle, and yield is higher, simple to operate, and technique is green, especially suitable for large-scale industrial production, therefore, has broad application prospects and market potential.

Description

A kind of preparation method of liquid phosphite antioxidant
Technical field
The invention belongs to auxiliary chemicals to synthesize field, more particularly to a kind of preparation method of liquid phosphite antioxidant.
Background technology
Antioxidant is to stabilize important auxiliary agent in fluoropolymer resin processing and application process, and its application is almost related to all poly- Compound and its product.Polymer product increase of production in China's is rapid in recent years, and this provides good for the development and application of antioxidant Good market prospects.Phosphite antioxidant is a kind of high-efficiency anti-oxidant of excellent performance, and it is steady can not only to improve Polymer Processing It is qualitative, and there is good color stability, heat-resistant stability and excellent hydrolytic Resistance, therefore in polyolefin, benzene second There is good application prospect in vinyl resin and engineering thermoplastic resin Polymer material.
Phosphite ester auxiliary antioxidant is the most active neck of variety development in polymer stabilising auxiliary agent the 1990s One of domain.New construction kind emerges in an endless stream during the decade, but by their chemical constitution it can be found that the phosphorous of these new constructions Most of acid esters includes substitution aromatic ring, and is occupied with pentaerythritol bis-phosphite spirane structure and bis-phenol phosphite ester structure It is more, illustrate that the focus of phosphorous acid esters auxiliary antioxidant technological development concentrates on and improve processing stability and improvement hydrolytic stability Two aspects.
Anacardol (Cardanol) be one kind from natural cashew nut shell oil through advanced technology refine form, can replace or Part replaces phenol to be used to manufacture epoxy hardener, liquid phenolic resin, liquid or powdered thermosetting phenolic resin, waist Fruit phenol is also had the characteristics that with its special chemical constitution:(1) contain benzene ring structure, there is resistance to elevated temperatures;(2) hydroxyl of polarity Base can provide wetting and activity of the system to contact surface;(3) carbon 15 straight chain of the meta containing unsaturated double-bond, it is good to provide system Toughness, excellent hydrophobicity and hypotonicity and from dryness.
In the prior art, United States Patent (USP) US7781623, US7825284 are disclosed from cashew nut shell oil extraction anacardol Technique.Anacardol had both had the property of phenols, had the property of alkene again;It will obtain hydrogenating cashew nut after anacardol catalytic hydrogenation Phenol, it has the property of phenols, has the flexibility of aliphatic compound again, and has the emulsification and increasing more superior than nonyl phenol Plasticity energy.At present, anacardol and its derivative be used to prepare epoxy hardener, phenolic resin, surfactant and demulsification more Agent etc., as Chinese patent 201110177345.0 discloses the preparation method of Cardanol Modified PF Resin, such as Chinese patent 200810042953.9 disclose purposes of the anacardol in epoxy resin cure, and and for example, United States Patent (USP) US6229054 is disclosed Hydrogenation anacardol synthesizes a kind of change of monohydroxy alkyl cashew nut phenol ether through reaction in the case where organic base does catalysts conditions with organic carbonate Compound.
The content of the invention
The present invention is intended to provide a kind of preparation method of new liquid phosphite antioxidant, inventor with phosphorus trichloride, Anacardol, isooctanol are reaction raw materials, and using methyl tricapryl ammonium chloride as catalyst, successively by under normal pressure, condition of negative pressure Gradient increased temperature reaction, and using di-n-butylamine, tri-n-butylamine carry out neutralization reaction, successfully synthesize product;Also, in the work In the implementation process of skill, excessive isooctanol, di-n-butylamine, tri-n-butylamine have obtained good recycling, therefore, the system Preparation Method cost is cheap, environment-friendly, is advantageous to large-scale industrial production.
Specifically, the invention provides a kind of preparation method of liquid phosphite antioxidant, it comprises the following steps:
S1:Phosphorus trichloride, anacardol, isooctanol are added into a reaction vessel, and adds the methyl three as catalyst Octyl group ammonium chloride, gradient increased temperature reaction;
S2:Isooctanol is added, continues to react;
S3:After reaction completely, the complete isooctanol of unreacted is distilled out, is reclaimed;
S4:Di-n-butylamine, tri-n-butylamine are added into the reaction vessel to carry out neutralization reaction, obtains product mixture;
S5:The complete di-n-butylamine of unreacted, tri-n-butylamine are distilled out, is reclaimed;
S6:Heat filtering, filtrate is taken, produce the liquid phosphite antioxidant.
Preferably, the gradient increased temperature reaction in the S1 of above-mentioned preparation method includes:
First stage:At ambient pressure, heat temperature raising, temperature in the reaction vessel is made to rise to 40~50 DEG C, then, 40 Insulation reaction at~50 DEG C;
Second stage:Heat temperature raising, temperature in the reaction vessel is set to rise to 130~140 DEG C, then, 130~140 Insulation reaction at DEG C;
Phase III:Start vavuum pump to vacuumize so that the pressure in the reaction vessel is -60~-70kpa, temperature For 110~120 DEG C, back flow reaction.
What deserves to be explained is in above-mentioned S1, S2 course of reaction, hydrogen chloride gas generation is had, these generation chlorinations Hydrogen is discharged into chlorine hydride absorption system, so as to generate hydrochloric acid.
It is further preferred that in above-mentioned preparation method, in the first stage, the duration of the heat temperature raising is 1~1.5 hour, the duration of the insulation reaction was 1.5~2 hours.
It is further preferred that in above-mentioned preparation method, in the second stage, the duration of the heat temperature raising is 1.5~2 hours, the duration of the insulation reaction was 1.5~2 hours.
It is further preferred that in above-mentioned preparation method, in the phase III, the duration of the back flow reaction is 2.5~3.5 hours.
Preferably, in above-mentioned preparation method, S2 includes:Pressure in the reaction vessel is -40~-50kpa's Under the conditions of, the isooctanol added is added dropwise, and be added dropwise in 0.5 hour, then, adjust the pressure in the reaction vessel To -60~-70kpa, and continuation back flow reaction 2.5~3.5 hours at 120~130 DEG C.
Preferably, in above-mentioned preparation method, S3 includes:After reaction completely, in -99~-99.5kpa pressure and 160 At a temperature of~165 DEG C, the complete isooctanol of unreacted in the reaction vessel is distilled, reclaimed.
Preferably, in above-mentioned preparation method, S4 includes:Nitrogen (purity >=99.9%) is passed through into reaction vessel, will Recover in the reaction vessel to normal pressure, and add di-n-butylamine, tri-n-butylamine, neutralization reaction 0.5~1 is small at 80~90 DEG C When, obtain product mixture.
Preferably, in above-mentioned preparation method, S5 includes:Under conditions of 110~120 DEG C and -99~-99.5kpa, from The complete di-n-butylamine of unreacted, tri-n-butylamine are distilled out in the product mixture, is reclaimed.
Preferably, the operation temperature of the heat filtering described in the S6 of above-mentioned preparation method is 70~80 DEG C.
Preferably, the anacardol in the S1 of above-mentioned preparation method, the matter of the phosphorus trichloride and the isooctanol Amount is than being 3~3.24:1.3~1.4:1~1.08, also, the quality of the methyl tricapryl ammonium chloride is described different in S1 The 2% of the quality of octanol.
Preferably, the quality for the isooctanol added in the S2 of above-mentioned preparation method is the quality of the isooctanol in S1 50%.
Preferably, the quality of the di-n-butylamine in the S4 of above-mentioned preparation method is the matter of the isooctanol in S1 The 2.5~2.7% of amount, the quality of the tri-n-butylamine are the 3.7~3.9% of the quality of the isooctanol in S1.
What deserves to be explained is pressure listed in the present invention is gauge pressure.
In summary, the preparation method of liquid phosphite antioxidant provided by the invention is with phosphorus trichloride, anacardol, different Octanol is reaction raw materials, and using methyl tricapryl ammonium chloride as catalyst, dexterously using gradient increased temperature react with it is anti-stage by stage Answer technique, target product has successfully been made, i.e., described liquid phosphite antioxidant;The preparation method process route is short, instead Mild condition is answered, yield is higher, simple to operate, and technique is green, especially suitable for large-scale industrial production, therefore, tool Have broad application prospects and market potential.
Embodiment
With reference to embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiment party Formula.
According to a kind of preparation method of liquid phosphite antioxidant of the present invention, comprise the following steps:
S1:Phosphorus trichloride, anacardol, isooctanol are added into a reaction vessel, and adds the methyl three as catalyst Octyl group ammonium chloride, gradient increased temperature reaction;
S2:Isooctanol is added, continues to react;
S3:After reaction completely, the complete isooctanol of unreacted is distilled out, is reclaimed;
S4:Di-n-butylamine, tri-n-butylamine are added into the reaction vessel to carry out neutralization reaction, obtains product mixture;
S5:The complete di-n-butylamine of unreacted, tri-n-butylamine are distilled out, is reclaimed;
S6:Heat filtering, filtrate is taken, produce the liquid phosphite antioxidant.
In a preferred embodiment, the gradient increased temperature reaction in S1 includes:
First stage:At ambient pressure, heat temperature raising, temperature in the reaction vessel is made to rise to 40~50 DEG C, then, 40 Insulation reaction at~50 DEG C;In this stage, there is hydrogen chloride gas generation, these generation hydrogen chloride are discharged into hydrogen chloride tail gas suction Receive in bottle, be converted into hydrochloric acid;
Second stage:Heat temperature raising, temperature in the reaction vessel is risen to 130~140 DEG C, now react more acute Strong, the amount of caused hydrogen chloride is larger, so as to which bubbling is more in hydrogen chloride tail gas absorption bottle;Then, protected at 130~140 DEG C Temperature reaction, now, the amount of the hydrogen chloride of generation significantly reduces;
Phase III:Start vavuum pump to vacuumize so that the pressure in the reaction vessel is -60~-70kpa, temperature For 110~120 DEG C, back flow reaction;In this stage, isooctanol condensed device condensation repeatedly, realizes back flow reaction.
In a further preferred embodiment, in the first stage, duration of the heat temperature raising for 1~ 1.5 hours, the duration of the insulation reaction was 1.5~2 hours.
In a further preferred embodiment, in the second stage, the duration of the heat temperature raising is 1.5 ~2 hours, the duration of the insulation reaction was 1.5~2 hours.
In a further preferred embodiment, in the phase III, the duration of the back flow reaction is 2.5 ~3.5 hours.
In a preferred embodiment, S2 includes:The condition that pressure in the reaction vessel is -40~-50kpa Under, the isooctanol added is added dropwise, and be added dropwise in 0.5 hour, then, adjusts pressure in the reaction vessel to -60 ~-70kpa, and continuation back flow reaction 2.5~3.5 hours at 120~130 DEG C;In other words, it is unreacted different in this S2 Octanol still condensed device condensation repeatedly, reaction is continued to participate in by backflow.
In a preferred embodiment, S3 includes:After reaction completely, in -99~-99.5kpa pressure and 160~165 At a temperature of DEG C, the complete isooctanol of unreacted in the reaction vessel is distilled, reclaimed;Wherein, the isooctanol of recovery can Further it is re-used in S1 or/and S2.
In a preferred embodiment, S4 includes:Nitrogen (purity >=99.9%) is passed through into reaction vessel, will be described anti- Answer in container and recover to normal pressure, and add di-n-butylamine, tri-n-butylamine, neutralization reaction 0.5~1 hour, is obtained at 80~90 DEG C Product mixture.
In a preferred embodiment, S5 includes:Under conditions of 110~120 DEG C and -99~-99.5kpa, from described The complete di-n-butylamine of unreacted, tri-n-butylamine (i.e. excessive di-n-butylamine, tri-n-butylamine) are distilled out in product mixture, is returned Receive;Wherein, the di-n-butylamine of recovery, tri-n-butylamine further can be re-used in S4.
In a preferred embodiment, the operation temperature of the heat filtering described in S6 is 70~80 DEG C, also, the heat Filtering can remove the impurity remained in reaction solution and salinity.
In a preferred embodiment, the anacardol in S1, the quality of the phosphorus trichloride and the isooctanol Than for 3~3.24:1.3~1.4:1~1.08, also, the quality of the methyl tricapryl ammonium chloride is described different pungent in S1 The 2% of the quality of alcohol;In based on the further preferred embodiment of this, the anacardol, the trichlorine in S1 The mass ratio for changing phosphorus and the isooctanol is 3:1.365:1.
In a preferred embodiment, the quality for the isooctanol added in S2 is the quality of the isooctanol in S1 50%.
In a preferred embodiment, the quality of the di-n-butylamine in S4 is the quality of the isooctanol in S1 2.5~2.7%, the quality of the tri-n-butylamine is the 3.7~3.9% of the quality of the isooctanol in S1;Based on this A further preferred embodiment in, the quality of the di-n-butylamine in S4 is the quality of the isooctanol in S1 2.6%, the quality of the tri-n-butylamine is the 3.8% of the quality of the isooctanol in S1.
Furthermore it is noted that in the mistake for the preparation method for implementing liquid phosphite antioxidant of the present invention Cheng Zhong, it should be ensured that reaction system is isolated with ambient atmosphere, does not have extra air or moisture enters in reaction system with shadow Reaction is rung to be smoothed out.
Step in the preparation method of following liquid phosphite antioxidant is routine operation unless otherwise instructed, described Raw material can obtain from open commercial sources unless otherwise instructed.
Embodiment 1
A kind of liquid phosphite antioxidant is prepared according to following steps:
S1:It is pungent that 136.5g phosphorus trichlorides, 300g anacardols, 100g isooctanol and 2g methyl three are added into a reaction vessel Ammonium chloride;First, the low temperature temperature reaction of first stage is carried out:At ambient pressure, heat temperature raising 1 hour, hold the reaction Temperature rises to 40~50 DEG C in device, then, insulation reaction 1.5 hours at 40~50 DEG C;Then, the high temperature of second stage is carried out Temperature reaction:Heat temperature raising 2 hours, temperature in the reaction vessel is set to rise to 130~140 DEG C, then, at 130~140 DEG C Insulation reaction 1.5 hours;Then, the vacuum back-flow reaction of phase III is carried out:Start vavuum pump to vacuumize so that the reaction Pressure in container is -60~-70kpa (G), and temperature is 110~120 DEG C, back flow reaction 2.5 hours.
S2:Under conditions of pressure in the reaction vessel is -40~-50kpa (G), isooctanol is separately added, specifically For 50g isooctanol is added dropwise, and be added dropwise in 0.5 hour, then, adjust pressure in the reaction vessel to -60~- 70kpa (G), and continuation back flow reaction 3 hours at 120~130 DEG C.
S3:After reaction completely, at a temperature of -99~-99.5kpa (G) pressure and 160~165 DEG C, by the reaction The complete isooctanol of unreacted distills in container, recovery.
S4:Nitrogen (purity >=99.9%) is passed through into reaction vessel, will be recovered in the reaction vessel to normal pressure, and add Enter 2.6g di-n-butylamines, 3.8g tri-n-butylamines, neutralization reaction 0.5 hour, obtains product mixture at 80~90 DEG C.
S5:Under conditions of 110~120 DEG C and -99~-99.5kpa (G), distilled out not from the product mixture Di-n-butylamine, the tri-n-butylamine reacted, recovery;Distillation time therein control is 1 hour, with ensure by unreacted it is complete two N-butylamine, tri-n-butylamine all distill.
S6:Implement heat filtering, the impurity remained in reaction solution and salinity (common 8.6g) under 70~80 DEG C of operation temperature It is trapped and removes, take filtrate, obtains liquid as clear as crystal and with certain viscosity, i.e., described liquid phosphite antioxidant 448.8g yield 98.2%.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, it is of the invention and unlimited It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and Modification, all should be contained within the scope of the invention.

Claims (13)

1. a kind of preparation method of liquid phosphite antioxidant, it is characterised in that comprise the following steps:
S1:Phosphorus trichloride, anacardol, isooctanol are added into a reaction vessel, and adds the methyl trioctylphosphine as catalyst Ammonium chloride, gradient increased temperature reaction;
S2:Isooctanol is added, continues to react;
S3:After reaction completely, the complete isooctanol of unreacted is distilled out, is reclaimed;
S4:Di-n-butylamine, tri-n-butylamine are added into the reaction vessel to carry out neutralization reaction, obtains product mixture;
S5:The complete di-n-butylamine of unreacted, tri-n-butylamine are distilled out, is reclaimed;
S6:Heat filtering, filtrate is taken, produce the liquid phosphite antioxidant.
2. the preparation method of liquid phosphite antioxidant according to claim 1, it is characterised in that described in S1 Gradient increased temperature reaction includes:
First stage:At ambient pressure, heat temperature raising, temperature in the reaction vessel is made to rise to 40~50 DEG C, then, 40~50 Insulation reaction at DEG C;
Second stage:Heat temperature raising, temperature in the reaction vessel is set to rise to 130~140 DEG C, then, at 130~140 DEG C Insulation reaction;
Phase III:Start vavuum pump to vacuumize so that the pressure in the reaction vessel is -60~-70kpa, temperature 110 ~120 DEG C, back flow reaction.
3. the preparation method of liquid phosphite antioxidant according to claim 2, it is characterised in that the first stage In, the duration of the heat temperature raising is 1~1.5 hour, and the duration of the insulation reaction is 1.5~2 hours.
4. the preparation method of liquid phosphite antioxidant according to claim 2, it is characterised in that the second stage In, the duration of the heat temperature raising is 1.5~2 hours, and the duration of the insulation reaction is 1.5~2 hours.
5. the preparation method of liquid phosphite antioxidant according to claim 2, it is characterised in that the phase III In, the duration of the back flow reaction is 2.5~3.5 hours.
6. the preparation method of liquid phosphite antioxidant according to claim 1, it is characterised in that S2 includes:Institute The pressure in reaction vessel is stated under conditions of -40~-50kpa, the isooctanol added to be added dropwise, and drip in 0.5 hour Finish, then, adjust the pressure in the reaction vessel to -60~-70kpa, and continue back flow reaction 2.5 at 120~130 DEG C ~3.5 hours.
7. the preparation method of liquid phosphite antioxidant according to claim 1, it is characterised in that S3 includes:Reaction After completely, at a temperature of -99~-99.5kpa pressure and 160~165 DEG C, by complete different of unreacted in the reaction vessel Octanol distills, recovery.
8. the preparation method of liquid phosphite antioxidant according to claim 1, it is characterised in that S4 includes:By institute State in reaction vessel and recover to normal pressure, and add di-n-butylamine, tri-n-butylamine, neutralization reaction 0.5~1 is small at 80~90 DEG C When, obtain product mixture.
9. the preparation method of liquid phosphite antioxidant according to claim 1, it is characterised in that S5 includes:110 Under conditions of~120 DEG C and -99~-99.5kpa, the complete di-n-butylamine of unreacted, three are distilled out from the product mixture N-butylamine, recovery.
10. the preparation method of liquid phosphite antioxidant according to claim 1, it is characterised in that described in S6 Heat filtering operation temperature be 70~80 DEG C.
11. the preparation method of liquid phosphite antioxidant according to claim 1, it is characterised in that the institute in S1 The mass ratio for stating anacardol, the phosphorus trichloride and the isooctanol is 3~3.24:1.3~1.4:1~1.08, also, it is described The quality of methyl tricapryl ammonium chloride is the 2% of the quality of the isooctanol in S1.
12. the preparation method of liquid phosphite antioxidant according to claim 1, it is characterised in that added in S2 Isooctanol quality be S1 in the isooctanol quality 50%.
13. the preparation method of liquid phosphite antioxidant according to claim 1, it is characterised in that the institute in S4 The quality for stating di-n-butylamine is the 2.5~2.7% of the quality of the isooctanol in S1, and the quality of the tri-n-butylamine is in S1 The isooctanol quality 3.7~3.9%.
CN201710843377.7A 2017-09-18 2017-09-18 A kind of preparation method of liquid phosphite antioxidant Pending CN107573373A (en)

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Cited By (1)

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Application publication date: 20180112