CN101955411B - Styrene polymerization restraining compound polymerization inhibitor - Google Patents
Styrene polymerization restraining compound polymerization inhibitor Download PDFInfo
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- CN101955411B CN101955411B CN 201010282417 CN201010282417A CN101955411B CN 101955411 B CN101955411 B CN 101955411B CN 201010282417 CN201010282417 CN 201010282417 CN 201010282417 A CN201010282417 A CN 201010282417A CN 101955411 B CN101955411 B CN 101955411B
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Abstract
The invention discloses a styrene polymerization restraining compound polymerization inhibitor, which is a polymerization inhibitor capable of restraining styrene polymerization at the temperature of 60 to 80 DEG C, and is characterized by restraining the styrene polymerization at the temperature of 80 to 100 DEG C by using para-tert-butylcatechol, ortho-tertiary-butyl 4,6-dinitrophenol and/or a high-efficiency polymerization inhibitor PI-70 as raw materials or by using the high-efficiency polymerization inhibitor PI-70, the ortho-tertiary-butyl 4,6-dinitrophenol and/or hydroquinone as raw materials. The styrene polymerization restraining compound polymerization inhibitor can effectively restrain the polymerization speed and polymerization time of styrene and has good polymerization restraining effect, low cost, low toxicity and low viscosity.
Description
One, technical field
The present invention relates to suppress the stopper of styrene polymerization, relate in particular to the compound polymerization inhibitor that is used in the phenyl ethylene rectification process and the field of preservation.
Two, background technology
Vinylbenzene is the important basic material of petroleum chemical industry, and purposes is very extensive, is mainly used in styrene series resin and styrene-butadiene rubber(SBR), can be used for industries such as pharmacy, coating, weaving and ore dressing in addition.
Easy autohemagglutination under the vinylbenzene normal temperature, refining at it, store and each stage of using polymerization in all can polymerization, especially treating process, can cause loss of monomer, line clogging, cause the monomer production cost to raise, for this reason, must add stopper to suppress its polymerization.
The first-generation stopper that 70～eighties of 20th century uses is with 2,2, 4-dinitrophenol (DNP), Resorcinol and benzoquinones are representative, the toxicity of this class stopper is big, the poly-efficient of resistance is lower, poor heat resistance, environmental pollution are serious, seldom use at present, but it is composite with s-generation stopper to can be used as auxiliary, obtains the better Compositional type stopper of polymerization inhibition effect.After the eighties in 20th century,, reduced the toxicity of DNP by in the DNP structure, introducing groups such as methyl, ethyl and butyl, improved the solubleness of DNP in vinylbenzene, 2,6-dinitro-p-cresol DNPC and o-tert-butyl-4,6-dinitrophenol(DNP) DNBP is the representative of this type of stopper.
Since the nineties in 20th century, some new and effective low toxicity stoppers begin on styrene device on probation, these stoppers are many by 2～3 kinds of composite forming of component, the poly-efficient of resistance is apparently higher than DNBP or DNPC stopper, consumption also further reduces, thereby reduced production cost, also solved preceding two generation stopper be insoluble in vinylbenzene, reinforced difficulty, toxicity is big and problem such as contaminate environment.The organism retarder is composite forms by piperidine nitroxide free-radical master stopper and other for this class stopper major part.Piperidine nitroxide free-radical stopper and substituted hydroxylamines stopper all are the stoppers of the recent novel stabilising of finding, have high temperature resistant, easy dissolving, low toxicity, nothing corrosion and all have advantage such as polymerization inhibition performance at gas-liquid two-phase, but because the price comparison height of azanol class and piperidines, and these two kinds of compound high temperature are volatile, the liquid phase weak effect, and prepared stopper viscosity is bigger, and resistance is big, therefore the energy consumption height has increased cinnamic production cost.
Three, summary of the invention
The present invention is for avoiding above-mentioned existing in prior technology weak point, the compound polymerization inhibitor of the inhibition styrene polymerization that a kind of polymerization inhibition effect is good, cost is low, toxicity is little, viscosity is low is provided, in the hope of effectively suppressing cinnamic polymerization velocity and polymerization time, in petroleum chemical industry, effectively prolong the working time of styrene device, improve the output and the quality of styrene product, make the production process of styrene device obtain better economic benefit, also this problem of polymerization is taken place easily vinylbenzene in the transportation and proposed better terms of settlement.
Technical solution problem of the present invention adopts following technical scheme:
The present invention is to have following arbitrary form 60～80 ℃ of characteristics that suppress the stopper of styrene polymerization down:
Form one: the effective constituent of described stopper consists of: A component, B component and C component; Press mass ratio, the A component: the B component: the C component is 0.2～0.5: 0.2～0.5: 0.2～0.5;
Form two: the effective constituent of described stopper is formed or is: A component and B component, and press mass ratio, the A component: the B component is 0.1～3: 1;
Form three: the effective constituent of described stopper consists of: A component and C component, and press mass ratio, the A component: the C component is 0.1～3: 1;
Wherein, described A component is tert-butyl catechol TBC; The B component is an o-tert-butyl 4,6-dinitrophenol(DNP) DNBP; The C component is stopper PI-70.
Also be 60～80 ℃ of characteristics that suppress the stopper of styrene polymerization down:
In the described form one, press mass ratio, the A component: the B component: the C component is 1: 1: 1;
In the described form two, press mass ratio, the A component: the B component is 1: 3;
In the described form three, press mass ratio, the A component: 1: 3 of C component.
The present invention is to have following arbitrary form 80～100 ℃ of characteristics that suppress the stopper of styrene polymerization down:
Form one: the effective constituent of described stopper consists of: B component, C component and D component, and press mass ratio, the B component: the C component: the D component is 0.2～0.5: 0.2～0.5: 0.2～0.5;
Form two: the effective constituent of described stopper consists of: B component and C component, and press mass ratio, the B component: the C component is 0.1～3: 1;
Form three: the effective constituent of described stopper consists of: C component and D component, and press mass ratio, the C component: the D component is 0.1～3: 1;
Wherein: the B component is an o-tert-butyl 4,6-dinitrophenol(DNP) DNBP; Described C component is stopper PI-70; Described D component is Resorcinol HQ;
Also be 80～100 ℃ of characteristics that suppress the stopper of styrene polymerization down:
In the described form one, press mass ratio, the B component: the C component: the D component is 2: 2: 1;
In the described form two, press mass ratio, the B component: the C component is 1: 1;
In the described form three, press mass ratio, the C component: the D component is 1: 1.
The present invention is the compound polymerization inhibitor that suppresses styrene polymerization under differing temps, and compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention uses the compound polymerization inhibitor that the modification of s-generation stopper obtains, because synergy makes the composite stopper effect that obtains significantly better than single component; Because used stopper is common styrene polymerization inhibitor, so cost is lower; Employed stopper has only the toxicity of Resorcinol a little bigger relatively, and all the other stoppers all are nontoxic; Except that Resorcinol, all the other stoppers all are liquid, so the mixture viscosity that obtains is lower.
2, the preparation method of compound polymerization inhibitor of the present invention is simple, directly each component is at room temperature stirred in the ratio of setting to get final product.
Four, embodiment
Embodiment 1～14th, prepares the stopper of different components and proportioning and be applied in the styrene polymerization reaction under 60～80 ℃ wherein to contain the contrast experiment to observe and polymerization inhibition effect.
Under 60～80 ℃ of temperature, take by weighing among a certain amount of initiator A IBN, peace bottle that stopper joins dilatometer after refining, the styrene monomer of measuring after an amount of refining with graduated cylinder adds again, puts into heated polymerizable in the water bath with thermostatic control after the kapillary of dilatometer and peace bottle are connected.Write down the maximum height that liquid level rises, per again height of writing down liquid level in 5～10 minutes, and transformation efficiency mapped to the time, result of implementation is as shown in table 1.
Embodiment 1 is the blank contrast experiment who does not add stopper.
Embodiment 2 be single component stopper HQ mass concentration consumption from 200～500ppm, polymerization inhibition effect was best when mass concentration was 300ppm.
Embodiment 3 be single component stopper TBC mass concentration consumption from 200～500ppm, polymerization inhibition effect was best when mass concentration was 400ppm.
Embodiment 4 be single component stopper DNBP mass concentration consumption from 200～500ppm, polymerization inhibition effect was best when mass concentration was 500ppm.
Embodiment 5 be single component stopper PI-70 mass concentration consumption from 200～500ppm, polymerization inhibition effect was best when mass concentration was 350ppm.
Embodiment 6,7,8 is two component stopper TBC: the DNBP mass ratio is from 0.1～3: 1, and total mass concentration is 400ppm, proportioning is that 1: 3 o'clock polymerization inhibition effect is best.
Embodiment 9,10,11 is two component stopper TBC: the PI-70 mass ratio is from 0.1～3: 1, and total mass concentration is 400ppm, proportioning is that 1: 3 o'clock polymerization inhibition effect is best.
Embodiment 12,13,14 is three component stopper TBC: DNBP: the PI-70 mass ratio is from 0.2～0.5: 0.2～0.5: 0.2～0.5, and total mass concentration is 400ppm, proportioning is that 1: 1: 1 o'clock polymerization inhibition effect is best.
Table 1 is the comparison of compound polymerization inhibitor of the present invention and other stopper polymerization inhibition effects down in T=60～80 ℃
* the mass concentration in the table is to be solvent with the styrene monomer, and stopper is that solute calculates.
What this table was selected is that (selection of mass concentration consumption is that the best polymerization inhibition effect of 200～500ppm), two component stoppers and three component stoppers compares to the single component stopper, and total mass concentration is 400ppm.As can be seen from the table, TBC: DNBP=1 in two component stoppers are composite: 3, TBC: PI-70=1: the polymkeric substance transformation efficiency was minimum in 3 o'clock, and the poly-time of resistance is the longest; TBC: DNBP: PI-70=1 when three component stoppers are composite: the polymkeric substance transformation efficiency was minimum in 1: 1 o'clock.
Embodiment 15～28th, prepare the stopper of different components and proportioning and be applied in the styrene polymerization reaction under 80～100 ℃ wherein to contain the contrast experiment to observe and polymerization inhibition effect.
Under 80～100 ℃ of temperature, take by weighing among a certain amount of initiator A IBN, peace bottle that stopper joins dilatometer after refining, the styrene monomer of measuring after an amount of refining with graduated cylinder adds again, puts into heated polymerizable in the water bath with thermostatic control after the kapillary of dilatometer and peace bottle are connected.Write down the maximum height that liquid level rises, per again height of writing down liquid level in 5/10 minute, and transformation efficiency mapped to the time, result of implementation is as shown in table 2.
Embodiment 15 is the blank contrast experiments that do not add stopper.
Embodiment 16,17,18 is two component stopper DNBP: the PI-70 mass ratio is from 0.1～3: 1, and total mass concentration is 400ppm, proportioning is that 1: 1 o'clock polymerization inhibition effect is best.
Embodiment 19,20,21 is two component stopper PI-70: the HQ mass ratio is from 0.1～3: 1, and total mass concentration is 400ppm, proportioning is that 1: 1 o'clock polymerization inhibition effect is best.
Embodiment 22 is two component stopper HQ: the DNBP mass ratio is from 0.1～3: 1, and total mass concentration is 400ppm, proportioning is that 1: 3 o'clock polymerization inhibition effect is best.
Embodiment 23 is two component stopper HQ: the TBC mass ratio is from 0.1～3: 1, and total mass concentration is 400ppm, proportioning is that 1: 3 o'clock polymerization inhibition effect is best.
Embodiment 24,25,26 is two component stopper TBC: the DNBP mass ratio is from 0.1～3: 1, and total mass concentration is 400ppm, proportioning is that 1: 1 o'clock polymerization inhibition effect is best.
Embodiment 27 is two component stopper TBC: the PI-70 mass ratio is from 0.1～3: 1, and total mass concentration is 400ppm, proportioning is that 1: 3 o'clock polymerization inhibition effect is best.
Embodiment 28,29,30 is three component stopper DNBP: PI-70: the HQ mass concentration ratio is from 0.2～0.5: 0.2～0.5: 0.2～0.5, and total mass concentration is 400ppm, proportioning is that 2: 2: 1 o'clock polymerization inhibition effects are best.
Table 2 is the comparison of compound polymerization inhibitor of the present invention and other stopper polymerization inhibition effects down in T=80～100 ℃
* the mass concentration in the table is to be solvent with the styrene monomer, and stopper is that solute calculates.
Because polymerization inhibition effect and poly-time of resistance in T=80～100 ℃ following single component all are poor, so what select here is that they are composite, total mass concentration is 400ppm, and what this table was selected is the best polymerization inhibition effect comparison of two component stoppers and three component stoppers.As can be seen from the table, in two component stoppers are composite, PI-70: HQ=1: 1, DNBP: PI-70=1: the polymkeric substance transformation efficiency was minimum in 1 o'clock, and the poly-time of resistance is the longest; DNBP: PI-70: HQ=2 during three component stoppers are composite: the poly-time of resistance in 2: 1 o'clock is longer, and the polymkeric substance transformation efficiency is minimum.
Claims (4)
1. one kind at 60～80 ℃ of stoppers that suppress down styrene polymerizations, it is characterized in that having following arbitrary form:
Form one: the effective constituent of described stopper consists of: A component, B component and C component; Press mass ratio, the A component: the B component: the C component is 0.2～0.5: 0.2～0.5: 0.2～0.5;
Form two: the effective constituent of described stopper consists of: A component and B component, and press mass ratio, the A component: the B component is 0.1～3: 1;
Form three: the effective constituent of described stopper consists of: A component and C component, and press mass ratio, the A component: the C component is 0.1～3: 1;
Wherein, described A component is tert-butyl catechol TBC; The B component is an o-tert-butyl 4,6-dinitrophenol(DNP) DNBP; The C component is stopper PI-70.
2. according to claim 1 at 60～80 ℃ of stoppers that suppress styrene polymerization down, it is characterized in that:
In the described form one, press mass ratio, the A component: the B component: the C component is 1: 1: 1;
In the described form two, press mass ratio, the A component: the B component is 1: 3;
In the described form three, press mass ratio, the A component: 1: 3 of C component.
3. one kind at 80～100 ℃ of stoppers that suppress down styrene polymerizations, it is characterized in that having following arbitrary form:
Form one: the effective constituent of described stopper consists of: B component, C component and D component, and press mass ratio, the B component: the C component: the D component is 0.2～0.5: 0.2～0.5: 0.2～0.5;
Form two: the effective constituent of described stopper consists of: B component and C component, and press mass ratio, the B component: the C component is 0.1～3: 1;
Form three: the effective constituent of described stopper consists of: C component and D component, and press mass ratio, the C component: the D component is 0.1～3: 1;
Wherein: the B component is an o-tert-butyl 4,6-dinitrophenol(DNP) DNBP; Described C component is stopper PI-70; Described D component is Resorcinol HQ;
4. according to claim 3 at 80～100 ℃ of stoppers that suppress styrene polymerization down, it is characterized in that:
In the described form one, press mass ratio, the B component: the C component: the D component is 2: 2: 1;
In the described form two, press mass ratio, the B component: the C component is 1: 1;
In the described form three, press mass ratio, the C component: the D component is 1: 1.
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| CN109232160A (en) * | 2018-10-29 | 2019-01-18 | 江苏常青树新材料科技有限公司 | A kind of compound polymerization inhibitor applied to divinylbenzene distillation system |
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| CN1974503A (en) * | 2006-12-13 | 2007-06-06 | 大连理工大学 | High efficiency composite polymerization inhibitor for refining styrene and its application |
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