CN104557846A - Polymerization inhibitor for rectifying epsilon-caprolactone - Google Patents

Polymerization inhibitor for rectifying epsilon-caprolactone Download PDF

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Publication number
CN104557846A
CN104557846A CN201410694833.2A CN201410694833A CN104557846A CN 104557846 A CN104557846 A CN 104557846A CN 201410694833 A CN201410694833 A CN 201410694833A CN 104557846 A CN104557846 A CN 104557846A
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CN
China
Prior art keywords
caprolactone
rectifying
polymerization inhibitor
stopper
polymerzation inhibitor
Prior art date
Application number
CN201410694833.2A
Other languages
Chinese (zh)
Inventor
李健
郭畅
王平
芮桂生
葛九敢
Original Assignee
江苏红太阳新材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 江苏红太阳新材料有限公司 filed Critical 江苏红太阳新材料有限公司
Priority to CN201410694833.2A priority Critical patent/CN104557846A/en
Publication of CN104557846A publication Critical patent/CN104557846A/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D313/00Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
    • C07D313/02Seven-membered rings
    • C07D313/04Seven-membered rings not condensed with other rings

Abstract

The invention discloses a compound polymerization inhibitor for rectifying epsilon-caprolactone. The compound polymerization inhibitor comprises the following components: a polymerization inhibitor monomer A and a polymerization inhibitor monomer B, wherein the polymerization inhibitor monomer A is N,N-diethylhydroxylamine (DEHA) and the polymerization inhibitor monomer B is one of tert-butyl catechol (TBC), o-nitrodiphenol (ONP) and hydroquinone. According to the compound polymerization inhibitor disclosed by the invention, the safety in production is enhanced by virtue of a synergistic effect of different polymerization inhibitor monomers, and meanwhile, the product purity of refined epsilon-caprolactone is improved, and polymerization reaction is reduced.

Description

A kind of stopper for 6-caprolactone rectifying

Technical field

The present invention relates to the production technique of 6-caprolactone, particularly relate to a kind of for the composite polymerzation inhibitor in 6-caprolactone distillation operation process.

Background technology

6-caprolactone is a kind of important organic synthesis intermediate, by the polyvalent alcohol of the derivative obtained after 6-caprolactone open loop as caprolactone modification, caprolactone Acrylic Acid Monomer, caprolactone polymers is successfully used as chemical intermediate and properties-correcting agent, is used for improving the performance of the polymkeric substance such as PU, vinylformic acid.The main application of current 6-caprolactone is produced polycaprolactone and generates multipolymer with other lipids.Polycaprolactone has biodegradability, is mainly used in medical sanitary equipment and high added value wrapping material at present, has vast potential for future development, belong to Green Product in degradable plastics field.

The synthesis of 6-caprolactone also exists larger technical barrier in the security of producing and product stability etc., and synthetic technology difficulty is large, and the stability solving security in producing and product prepares the key of 6-caprolactone.Such as 6-caprolactone rectifying purge process, rectification temperature is usually at about 110-120 DEG C, now easily there is self-polymerization and the polymerization degree is wayward in 6-caprolactone, greatly affects the purity of its product, and the 6-caprolactone simultaneously after polymerization causes equipment to block safety problem occurs.

Summary of the invention

For above-mentioned Problems existing, the invention provides and a kind ofly can greatly reduce the stopper that self-polymerization phenomenon occurs in 6-caprolactone distillation operation.

In order to achieve the above object, the technical solution used in the present invention is as follows: a kind of composite polymerzation inhibitor for 6-caprolactone rectifying, described composite polymerzation inhibitor comprises following component: stopper monomer A and stopper monomers B, described stopper monomer A is diethyl hydroxylamine (DEHA), and described stopper monomers B is the one in tert-butyl catechol (TBC), o-nitrophenol (ONP) and Resorcinol.

In composite polymerzation inhibitor of the present invention, stopper monomer A and stopper monomers B mass ratio are 1:0.5 ~ 2.By the synergy of compound stopper monomer A and monomers B, prevent 6-caprolactone from the phenomenon of being polymerized occurring in rectifying to reach, by stopper monomer A and the monomers B of this kind of proportioning, its good practical effect, the activity of diethyl hydroxylamine is promoted by inhibition collection monomers B, very few inhibition collection monomers B is less to its active improving performance, and too much stopper monomers B then affects the normal polymerization inhibition effect of stopper monomer A.

The using method of composite polymerzation inhibitor of the present invention is as follows: in the distillation operation of 6-caprolactone, under the protective condition of nitrogen, in tube sealing, adds 6-caprolactone and composite polymerzation inhibitor successively, and hot polymerization reaction 5h, finally obtains the 6-caprolactone after rectifying.

In the distillation operation of 6-caprolactone of the present invention, the mass ratio of composite polymerzation inhibitor and 6-caprolactone is 0.05 ~ 0.1:100.Greatly reduce 6-caprolactone by the composite polymerzation inhibitor of this consumption and easily self-polymerization effect occurs in rectifying, too much composite polymerzation inhibitor not only causes the waste of composite polymerzation inhibitor production cost, the impurity contained in the product simultaneously obtained increases, and very few composite polymerzation inhibitor then can not reach good polymerization inhibition effect.

The invention has the advantages that: 6-caprolactone easily self-polymerization occurs in rectifying, autopolymer can seriously cause equipment to block, and brings threat to production.Thus industrially for avoiding due to the fault that autohemagglutination brings in rectifying, under must adding this temperature of stopper easily there is self-polymerization in 6-caprolactone, causes equipment to block, and affect end product quality.Composite polymerzation inhibitor of the present invention, by adjustment single stopper proportioning and composition, strengthens the security in producing, improve simultaneously 6-caprolactone refine after product purity, decrease the generation of polyreaction.

Embodiment

Below in conjunction with embodiment, the present invention is described in further detail.

embodiment 1:

Be described with the static test under 120 DEG C of conditions.

In the tube sealing of N2 protection, add 100g 6-caprolactone, hot polymerization 5h, after being chilled to room temperature, detect 6-caprolactone content in product.

Calculate its polymer conversion and observe its apparent phenomenon; Experimental result is as shown in table 1.

embodiment 2:

Be described with the static test under 120 DEG C of conditions.

In the tube sealing of N2 protection, add 100g 6-caprolactone and DEHA0.08g, hot polymerization 5h, after being chilled to room temperature, detect 6-caprolactone content in product.

Calculate its polymer conversion and observe its apparent phenomenon; Experimental result is as shown in table 1.

embodiment 3:

Be described with the static test under 120 DEG C of conditions.

In the tube sealing of N2 protection, add 100g 6-caprolactone, DEHA0.05g and TBC0.03g, hot polymerization 5h, after being chilled to room temperature, detect 6-caprolactone content in product.

Calculate its polymer conversion and observe its apparent phenomenon; Experimental result is as shown in table 1.

embodiment 4:

Be described with the static test under 120 DEG C of conditions.

In the tube sealing of N2 protection, add 100g 6-caprolactone, DEHA0.04g and ONP0.05g, hot polymerization 5h, after being chilled to room temperature, detect 6-caprolactone content in product.

Calculate its polymer conversion and observe its apparent phenomenon; Experimental result is as shown in table 1.

embodiment 5:

Be described with the static test under 120 DEG C of conditions.

At N 2add 100g 6-caprolactone, DEHA0.05g and Resorcinol 0.02g, hot polymerization 5h in the tube sealing of protection, after being chilled to room temperature, detect 6-caprolactone content in product.

Calculate its polymer conversion and observe its apparent phenomenon; Experimental result is as shown in table 1.

embodiment 6:

The experimental result of gained in embodiment 1-5 added up, the experimental result obtained is as shown in table 1, and wherein transformation efficiency % is the probability of 6-caprolactone polymerization reaction take place in rectifying.Its method of calculation are as follows:

Polymer conversion=(residue 6-caprolactone-reactant 6-caprolactone)/reactant 6-caprolactone × 100%

Table 1 experimental result

Experimental result from embodiment 1 to 5 gained: after employing composite polymerzation inhibitor of the present invention, greatly reduce the probability of 6-caprolactone polymerization reaction take place, simultaneously compared to single stopper, it is by the synergy between different stopper monomer, further reduce the probability of 6-caprolactone polymerization reaction take place, improve 6-caprolactone refine after product purity, after rectification process completes simultaneously, the good flowing properties of product, conveniently collect, be not easily sticky in reaction vessel, cleaning is convenient, strengthen the security in producing, practical function is better.

It should be noted that, above-mentioned is only preferred embodiment of the present invention, is not used for limiting protection scope of the present invention, and equivalents done on the basis of above-described embodiment all belongs to protection scope of the present invention.

Claims (4)

1. the composite polymerzation inhibitor for 6-caprolactone rectifying, it is characterized in that, described composite polymerzation inhibitor comprises following component: stopper monomer A and stopper monomers B, described stopper monomer A is diethyl hydroxylamine (DEHA), and described stopper monomers B is the one in tert-butyl catechol (TBC), o-nitrophenol (ONP) and Resorcinol.
2., as claimed in claim 1 for the composite polymerzation inhibitor of 6-caprolactone rectifying, it is characterized in that, in described composite polymerzation inhibitor, stopper monomer A and stopper monomers B mass ratio are 1:0.5 ~ 2.
3. as claimed in claim 1 or 2 for the composite polymerzation inhibitor of 6-caprolactone rectifying; it is characterized in that; the using method of described composite polymerzation inhibitor is as follows: in the distillation operation of 6-caprolactone; under the protective condition of nitrogen; 6-caprolactone and composite polymerzation inhibitor is added successively in tube sealing; hot polymerization reaction 5h, finally obtains the 6-caprolactone after rectifying.
4., as claimed in claim 3 for the composite polymerzation inhibitor of 6-caprolactone rectifying, it is characterized in that, in the distillation operation of described 6-caprolactone, the mass ratio of composite polymerzation inhibitor and 6-caprolactone is 0.05 ~ 0.1:100.
CN201410694833.2A 2014-11-27 2014-11-27 Polymerization inhibitor for rectifying epsilon-caprolactone CN104557846A (en)

Priority Applications (1)

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CN201410694833.2A CN104557846A (en) 2014-11-27 2014-11-27 Polymerization inhibitor for rectifying epsilon-caprolactone

Publications (1)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4360682A (en) * 1979-05-23 1982-11-23 Deutsche Gold- Und Silberscheideanstalt Vormals Roessler Stabilizing caprolactones with dihydroxybenzenes
US4409408A (en) * 1982-09-24 1983-10-11 Atlantic Richfield Company Inhibiting polymerization of vinyl aromatic monomers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4360682A (en) * 1979-05-23 1982-11-23 Deutsche Gold- Und Silberscheideanstalt Vormals Roessler Stabilizing caprolactones with dihydroxybenzenes
US4409408A (en) * 1982-09-24 1983-10-11 Atlantic Richfield Company Inhibiting polymerization of vinyl aromatic monomers

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Application publication date: 20150429