CN105017205B - Epsilon-caprolactone polymerization inhibitor and application thereof - Google Patents
Epsilon-caprolactone polymerization inhibitor and application thereof Download PDFInfo
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- CN105017205B CN105017205B CN201510422669.4A CN201510422669A CN105017205B CN 105017205 B CN105017205 B CN 105017205B CN 201510422669 A CN201510422669 A CN 201510422669A CN 105017205 B CN105017205 B CN 105017205B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
Abstract
The invention discloses an epsilon-caprolactone polymerization inhibitor and an application thereof; the polymerization inhibitor takes silicon-containing oxazolone as a main component and also includes a stabilizer and a dewatering agent. The polymerization inhibitor is applied in a cyclic-ester-structure compound polymerization inhibition process. The principle of the polymerization inhibitor comprises that once epsilon-caprolactone is subjected to loop opening to become hydroxycaproic acid, the polymerization inhibitor fixes and captures active hydroxyl with a nitrogen-silicon bond in preference to an alcohol hydroxyl and carboxy hydroxyl reaction, so as to avoid further triggering of the active hydroxyl; therefore, the polymerization inhibitor can greatly reduce the caprolactone storage costs and the downstream production rate, facilitates caprolactone storage and long-distance transportation, and has relatively high economic benefits. In addition, the polymerization inhibitor disclosed by the invention also has significant control on self polymerization of cyclic aliphatic polyester.
Description
Technical field
The invention belongs to chemical technology field, and in particular to a kind of 6-caprolactone polymerization inhibitor and its application.
Background technology
6-caprolactone (ε-CL) is a kind of important organic intermediate, is mainly used in synthesizing polycaprolactone, also can be with other
Esters copolymerization or blending and modifying；The polymer that copolymerization or blending and modifying are obtained has good thermoplasticity, molding processibility, biology
The compatibility, avirulence, medicine permeability and biological degradability, before the aspect such as material, environmentally friendly and medical has a wide range of applications
Scape, therefore, the study on the synthesis of ε-CL is further important.
Unguyed agent or during catalyst before the forming, the phenomenon of monomer spontaneous polymerization is referred to as autohemagglutination.Due in oneself
Ester is a kind of temperature sensitivity material, is easily polymerized to 2～10 molecule oligomer certainly at high temperature, and in ε-CL production processes, essence
Evaporate process temperature higher, ε-CL produce a certain degree of autohemagglutination, cause amount of waste to increase, production cost rises, and the height for producing
It is viscous fluid under boiling point waste room temperature, after placing a period of time, becomes solid, intractability is big, not only affects product polymerization to produce
Rate, is more easy to process line is caused to damage.
The maximum inducement of ε-CL autohemagglutinations comes from the residual water in system, and water can cause ε-CL unimolecule open loops, shape
Into hydroxycaproic acid.And the end alcoholic extract hydroxyl group nucleophilic attack ability of open-loop products is stronger, other ε-CL open loops can be further induced to enter
And oligomer is formed, while carboxylic hydroxyl is although the relative alcoholic extract hydroxyl group activity of activity is weaker, it may have certain initiating activity.Autohemagglutination principle
Such as following formula：
Different from conventional free radical polymerization inhibitor, the core technology of ε-CL polymerization inhibitors is that control terminal hydroxyl product is lived
Property, you can with hydroxyl reaction or chelating.Chinese Patent Application No. is：" 201310299617.3 ", a kind of entitled " caprolactone
Polymerization inhibitor and anti-polymerization method " patent of invention disclose the polymerization inhibitor and anti-polymerization method of a kind of caprolactone, polymerization inhibitor be primary amine,
Secondary amine or tertiary amine compounds, anti-polymerization method are, under the conditions of 0～200 DEG C, polymerization inhibitor to be added to caprolactone or containing caprolactone
Material in stirring mixing after, sealing preserve；The method is simple and easy to implement, and polymerization inhibitor consumption is few, polymerization inhibition effect is obvious；Should
Polymerization inhibitor can be greatly lowered the production cost of caprolactone, be easy to storage and the long-distance sand transport of caprolactone, while preventing ring
Border is polluted, with very big economic benefit.
Chinese Patent Application No. is：" 201410694833.2 ", a kind of entitled " compound resistance for 6-caprolactone rectification
The patent of invention of poly- agent " discloses a kind of composite polymerzation inhibitor for 6-caprolactone rectification, described composite polymerzation inhibitor include as
Lower component：Polymerization inhibitor monomer A and polymerization inhibitor monomer B, described polymerization inhibitor monomer A are diethyl hydroxylamine (DEHA), described resistance
Poly- agent monomer B is the one kind in tert-butyl catechol (TBC), ortho-nitrophenol (ONP) and hydroquinone；The compound resistance of the present invention
Poly- agent strengthens the safety in production by the synergism between different polymerization inhibitor monomers, while improve 6-caprolactone refining
Product purity afterwards, reduces the generation of polyreaction.
It is excellent hydroxyl agent for capturing, the especially easy alcoholysis of nitrogen silicon key containing silica reagent, above-mentioned end can be closed well
Alcoholic extract hydroxyl group and carboxylic hydroxyl.Meanwhile, polymerization inhibitor should be stablized, and be difficult the homopolymerization under ringopening polymerization conditions；Oxazolone is stable five yuan
Ring, Thermodynamically stable in theory will not be in open loop under acid-base condition, and structure is close with cyclic ester, can be dissolved in ε-CL well,
Ensure ε-CL not autohemagglutinations during rectification and storage.At present, the polymerization inhibitor of this kind of ε-CL and other cyclic esters does not have been reported that.
The content of the invention
The scheme inhibited to 6-caprolactone containing silica reagent without utilization for prior art by the present invention, and ε-CL are in essence
During evaporating and storing, a certain degree of autohemagglutination is also easy to produce, affects product polymerization yield rate, process line is caused to damage, therefore this
The purpose of invention is to provide for a kind of 6-caprolactone polymerization inhibitor for selecting oxazolone for avtive spot carrier.
The present invention for the solution technical scheme that adopts of above-mentioned technical problem is：
The invention discloses a kind of 6-caprolactone polymerization inhibitor, the polymerization inhibitor includes the compound with 1 structure of formula, also includes
Stabilizer and deicer：
Wherein, R1、R2、R3、R4、R5Elect C independently of one another as1-C10Alkyl, C3-C8Cycloalkyl group, C2-C8Alkene
Alkyl, C2-C5Alkynes base,R6、R7Elect C independently of one another as1-C5Alkyl, C1-
C5Alkoxyl or hydrogen atom, the compound with 1 structure of formula be siliceous oxazolone.Wherein, R1、R2、R3It is preferred that methyl or benzyl
Base；R4、R5It is preferred that hydrogen atom, C1～C6Chain alkyl, phenyl, benzyl or benzene oxygen ethyl.
Further, the stabilizer in 6-caprolactone polymerization inhibitor of the invention is trialkyl phosphorous acid, alkyl phosphorous acid, virtue
Diphosphorous acid compound that cyclic nonaromatics that fragrant race's phosphorous acid, space are obstructed, space are obstructed, hydroxy phenylpropionic acid, hydroxyl
Amino-compound that benzyl compounds, benzyl alcohol, alkylidene bisphenols, alkyl phenol, aminoacid, thioether, space are obstructed, hydroquinone
In one or more.Technical staff can add be obstructed (alkyl, aryl, phenolic group) hydrazides, virtue according to understanding in stabilizer
Fragrant race or aliphatic amide mono hydroxyeicosatetraenoic acid or dihydroxy acid, cyclic amides, aliphatic or aromatic hydrazone aldehyde or dihydrazone aldehyde, two acyls
Base hydrazide derivatives.
Further, the deicer in 6-caprolactone polymerization inhibitor of the invention is clay, aluminium oxide, silica gel, zeolite, chlorination
One or more in calcium, Calcium Carbonate, sodium sulfate, calcium bicarbonate, sodium bicarbonate, potassium bicarbonate.
Further, the mass ratio of the compound with 1 structure of formula of the invention and 6-caprolactone monomer is 1: 100～1:
15,000, the monomer of 6-caprolactone is that purity is higher after the caprolactone crude product or rectification obtained in caprolactone production process
Product.Compound with 1 structure of formula is 1: 0.05～1: 0.1 with the mass ratio of stabilizer；Compound with 1 structure of formula
Mass ratio with deicer is 1: 0.01～1: 0.2.
Present invention also offers application of the 6-caprolactone polymerization inhibitor during cyclic ester structural compounds inhibition, the cyclic ester
Structure includes one or more that can be selected from the cyclic compound monomer with 2 structure of formula：
Wherein, A is [- (CR8R9)-]；R8、R9Selected from H, the alkyl with 1～5 carbon atom and with 1～5 carbon original
Identical or different group in alkyl that is sub and being replaced by halogen atom or hydroxyl；X is selected from O or N.
Beneficial effect：
1st, the present invention is adopted first and 6-caprolactone is inhibited containing silica reagent, and selects oxazolone to be avtive spot first
Carrier, lot of experiments prove the present invention polymerization inhibitor there is good polymerization inhibition effect, filled up using containing silica reagent to ε-
Technological gap in terms of caprolactone inhibition；
2nd, the oligomeric pollution that polymerization inhibitor of the invention may occur during reducing storage and remote conveying, and substantially reduce
Cost, with significant economic benefit；
3rd, after polymerization inhibitor of the invention is used in rectification working process so that after the completion of rectification process, the mobile performance of product
It is good, conveniently to collect, be difficult to be sticky in reaction vessel, cleaning is convenient, strengthens the safety in production, and practical function is preferable.
4th, polymerization inhibitor disclosed by the invention, also has significant control to the autohemagglutination of Cyclic aliphatic polyester.
Specific embodiment
Technical scheme is described in further detail with reference to specific embodiment, but the protection of the present invention
Scope is not limited to this.
Embodiment 1～8
With siliceous oxazolone：Stabilizer：The mass ratio of deicer carrys out mixed configuration resistance for 1: 0.05: 0.1 component composition
Alkyl phosphorous acid, aromatic series phosphorous acid are selected in poly- agent, wherein stabilizer；Deicer selects Calcium Carbonate.
By 8 batches, respectively the 6-caprolactone of 5g is respectively placed in the flask of 50mL, it is each to add 1mg polymerization inhibitors, siliceous evil
From 8 kinds in table one, oil bath heating at 100 DEG C, isothermal reaction 10 hours, cooling, sample analysis 6-caprolactone contain oxazolone
Amount, calculates the conversion ratio (i.e. aggregate rate) of 6-caprolactone with this, and the experimental result of different polymerization inhibitors is shown in Table 1.
Aggregate rate under 1 different polymerization inhibitor effects of table
Controlled trial：The 6-caprolactone of 5g is respectively placed in the flask of 50mL, oil bath heating at 100 DEG C, isothermal reaction
10 hours, cooling, the content of sample analysis 6-caprolactone, the conversion ratio (i.e. aggregate rate) of 6-caprolactone is 82.2%.
Embodiment 9～15
7 batches, the respectively 6-caprolactone of 5g are respectively placed in the flask of 50mL, the resistance in each addition 1mg embodiments 1
Poly- agent, oil bath heating, the isothermal reaction 10 hours at 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, cooling,
The content of sample analysis 6-caprolactone, calculates the conversion ratio (i.e. aggregate rate) of 6-caprolactone, the experiment under different temperatures with this
The results are shown in Table 2.
Experimental result under 2 different temperatures of table
Embodiment 16～23
8 batches, the respectively 6-caprolactone of 5g are respectively placed in the flask of 50mL, add embodiment 2 in polymerization inhibitor 1g,
3g, 4g, 5g, 7g, 8g, 9g, 10g, oil bath heating, isothermal reaction 10 hours, cooling, the content of sample analysis 6-caprolactone, with
Calculating 6-caprolactone conversion ratio (i.e. aggregate rate), the experimental result of different polymerization inhibitor consumptions is shown in Table 3 for this.
3 different impacts of the polymerization inhibitor consumption to aggregate rate of table
Embodiment 24～27
By 4 batches, the cyclic ester of 4 kinds of 5g is placed in the flask of 50mL respectively, the polymerization inhibitor in each addition 1mg embodiments 3,
Oil bath heating at 120 DEG C, isothermal reaction 10 hours, cooling, the content of sample analysis cyclic ester calculate cyclic ester conversion ratio with this
(i.e. aggregate rate), the experimental result of different cyclic esters is shown in Table 4.
The inhibition of 4 different cyclic ester monomers of table
Tested from above-described embodiment, after adding the polymerization inhibitor of siliceous oxazolone, caprolactone polymerization rate significantly reduces (table
One).Under lower temperature (60 DEG C), more preferably, polymerization inhibitor Applicable temperature extensively, is adapted to production technology and storage process to polymerization inhibition effect
(table two).As polymerization inhibitor consumption increases, polymerization inhibition effect more notable (table three), it is contemplated that integrated cost is used.Except oneself
Lactone, the polymerization inhibitor in the present invention are generally applicable to the inhibition (table four) of other cyclic ester monomers.
It should be noted that the foregoing is only some embodiments of the present invention, the present invention is not intended to limit, it is all using equivalent
The technical scheme obtained by the mode of replacement or equivalent transformation, all falls within protection scope of the present invention.
Claims (8)
1. a kind of 6-caprolactone polymerization inhibitor, it is characterised in that the polymerization inhibitor includes the compound with 1 structure of formula and stabilizer
And deicer,
Wherein,
R1、R2、R3、R4、R5Elect C independently of one another as1～C10Alkyl, C3～C8Cycloalkyl group, C2～C8Alkylene, C2
～C5Alkynes base,
R6、R7Elect C independently of one another as1～C5Alkyl, C1～C5Alkoxyl or hydrogen atom.
2. 6-caprolactone polymerization inhibitor according to claim 1, it is characterised in that in the compound with 1 structure of formula
R1、R2、R3Elect methyl or benzyl independently of one another as；R4、R5Elect hydrogen atom, C independently of one another as1～C6Chain alkyl,
Phenyl, benzyl or benzene oxygen ethyl.
3. 6-caprolactone polymerization inhibitor according to claim 1, it is characterised in that the compound with 1 structure of formula is：
4. 6-caprolactone polymerization inhibitor according to claim 1, it is characterised in that the stabilizer is alkyl phosphorous acid, virtue
Diphosphorous acid compound that cyclic nonaromatics that fragrant race's phosphorous acid, space are obstructed, space are obstructed, hydroxy phenylpropionic acid, hydroxyl
Amino-compound that benzyl compounds, benzyl alcohol, alkylidene bisphenols, alkyl phenol, aminoacid, thioether, space are obstructed, hydroquinone
In one or more.
5. 6-caprolactone polymerization inhibitor according to claim 1, it is characterised in that the deicer is clay, aluminium oxide, silicon
One or more in glue, zeolite, calcium chloride, Calcium Carbonate, sodium sulfate, calcium bicarbonate, sodium bicarbonate, potassium bicarbonate.
6. 6-caprolactone polymerization inhibitor according to claim 1, it is characterised in that the compound with 1 structure of formula and ε-oneself
The mass ratio of internal ester monomer is 1:100～1:15,000；The mass ratio 1 of the compound with 1 structure of formula and stabilizer:0.05～
1:0.1；Compound with 1 structure of formula is 1 with the mass ratio of deicer:0.01～1:0.2.
7. according to the arbitrary described 6-caprolactone polymerization inhibitor of claim 1-6, it is characterised in that the polymerization inhibitor is in cyclic ester structure
Application during compound inhibition.
8. 6-caprolactone polymerization inhibitor according to claim 7, it is characterised in that the cyclic ester structure includes can be selected from tool
There are one or more in the cyclic compound monomer of 2 structure of formula：
Wherein,
A is [- (CR8R9)—]；R8、R9Selected from H, the alkyl with 1～5 carbon atom and with 1～5 carbon atom and by halogen
Identical or different group in the alkyl that atom or hydroxyl replace；X is selected from O or N.
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Effective date of registration: 20210928 Address after: No.36 Shuanggao Road, economic development zone, Gaochun District, Nanjing, Jiangsu Province Patentee after: Nanjing Guoxing Biotechnology Research Institute Co.,Ltd. Address before: No. 18, Fangshui East Road, chemical industry park, Liuhe District, Nanjing, Jiangsu 210047 Patentee before: JIANGSU HONGTAIYANG NEW MATERIAL Co.,Ltd. |