CN105131684B - Preparation method for the inhibition coating of aromatic olefin monomers - Google Patents
Preparation method for the inhibition coating of aromatic olefin monomers Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the inhibition coating for aromatic olefin monomers, belong to aromatic olefin monomers storing technology field.The present invention is under nitrogen protective condition, using EP828 types epoxy resin as raw material, adds ethers auxiliary agent, reacts and coating surface layer base-material is made；After carrying out heating stirring reaction according still further to the step described in prepares coating surface layer base-material, cooling, polymerization inhibitor is added into system, carry out insulation reaction, coating bottom strata base-material is made；Curing agent is added separately to be well mixed in above two base-material；Aromatic olefin monomers reservoir walls are brushed by the way of layering is brushed, first brushing bottom base-material forms primer coating, then brushing surface layer base-material forms surface layer coating.Polymerization inhibitor addition of the present invention is big, and coating inhibition duration length, coating dosage is few, and adhesive force is good, can effectively control the rate of release of polymerization inhibitor in coating, so as to reach the effect inhibited for a long time, fundamentally solves the polymerism during aromatic olefin monomers storage.
Description
Technical field
The present invention relates to a kind of preparation method of the inhibition coating for aromatic olefin monomers, belong to aromatic olefin monomers storage skill
Art field.
Background technology
Aromatic olefin monomers chemical property is active, such as styrene is a kind of important polymerized monomer, and it can be with self-polymerization
Or polymerize with other monomers, it is widely used in synthesis high polymer material, coating, medicine and other fields.Styrene is at ambient temperature
Slow thermal excitation polymerisation can occur.Therefore, when aromatic olefin monomers convey or store, it is necessary to polymerization inhibitor is added, with
Ensure product quality.
Conventional storage polymerization inhibitor be tert-butyl catechol (TBC), the tertiary amyl hydroquinones of 2,5- bis-, benzoquinones, to benzene
Diphenol, MEHQ etc., all it is crystalloid material under normal temperature.During storage, at a certain temperature, the part in storage tank
Aromatic olefin monomers can vaporize, condense in the top of tank, side wall, support, the mouth of pipe, on pipeline, as commonly called " dew ".
Polymerization inhibitor is practically free of in these volatilization steam, is easily polymerize very much, very big harmfulness is brought to production：Storage tank can be caused
Top facility, floss hole, monitoring instrument in nozzle and tank etc. block, tank deck polymer is in " stalactite " shape when serious；Portion
Divide gaseous monomer polymerization, cause the loss of monomer in storage tank；When liquid monomer and these polymer contacts, polymer can be molten
In liquid phase, the product in storage tank is polluted, causes product quality reduction or unqualified；In addition, also made troubles to turnaround of unit.
Therefore, domestic and foreign scholars are ground to the method for preventing from occurring gaseous monomer polymerization in aromatic olefin monomers storage tank
Study carefully, to solve the problem of lime set polymerization.For example, being painted to styrene tank top to improve surface flatness, use up lime set
Fall into soon in liquid phase；The projecting part of reservoir walls is reduced as far as possible, so as to reduce the attachment point of styrene lime set.But both
Method can not avoid the polymerization of the styrene lime set without polymerization inhibitor completely.
Pair DOW chemical companies of the U.S. (US4161554) describe a kind of method for preventing styrene from polymerizeing in storage tank, i.e.,
Reservoir walls carry out coating, and a certain polymerization inhibitor is added into coating, and such monomer is after coating surface condensation, the resistance in coating
Poly- agent separates out, so as to prevent the polymerization of reservoir walls styrene.Used coating is epoxy resin and inorganic silicon coating, is hindered
Poly- agent is hydroquinones, MEHQ or p-tert-Butylcatechol, and dosage is the 0.1%~40% of coating content, 5 months
Interior polymerization inhibitor still has release.But the document does not report the adhesive force change of coating after the Adding Way of polymerization inhibitor, polymerization inhibitor addition
Change, the painting way of coating, and the specific method of control polymerization inhibitor rate of release, laboratory period of supervision also only have 5 months.
CN101921162A is to carry out coating in fragrant alkene reservoir walls, and coating is made up of bottom, intermediate layer and surface layer, in
Interbed is the coating containing polymerization inhibitor.The invention inhibits coating, polymerization inhibitor by the way of layering is brushed, in reservoir walls brushing
It can be discharged from the coating of solidification, to prevent the polymerization of tank deck monomer lime set, the patent coating is by up of three layers, construction
Process is relatively complicated, but feed postition and the preparation method of inhibition coating without reference to polymerization inhibitor.
CN103508831A propositions carry out painting brush applied coating in vinyl monomer reservoir walls, and coating is also by bottom, centre
Layer and surface layer composition, bottom and surface layer are the coating without polymerization inhibitor, and intermediate layer is the coating containing polymerization inhibitor, and intermediate layer is applying
Prepared before brush according to following steps：(1) polymerization inhibitor is added in solvent and dissolved；(2) solution in (1) is added to coating material
In the base-material of material, it is stirred；(3) auxiliary material curing agent is added in the base-material containing polymerization inhibitor, after being stirred, applied
Brush.By way of first polymerization inhibitor dissolving is then added in base-material, coating adhesion is improved.
CN102876177A describes a kind of styrene storage inner-wall paint, is made up of component A and B component, component A and B groups
The weight ratio divided is 4:1, component A includes epoxy phenolics, mixed solvent, pigment, filler, polymerization inhibitor, dispersant, anti-settling
Agent, B component include epoxy hardener, n-butanol.Polymerization inhibitor is 2,5- di-tert-butyl hydroquinones, and curing agent is cardanol epoxy
Curing agent or aromatic amine epoxy curing agent.Coating is made up of priming paint, intermediate coat and finish paint, and intermediate coat contains polymerization inhibitor.But the document
Squeegeeing step is more, does not disclose Paint preparation technology condition, and coating polymerization inhibitor used, curing agent etc. are significantly different with the present invention,
Polymerization inhibitor is using the Adding Way after first being dissolved with solvent, complex procedures, the attachment of coating after also being added without report polymerization inhibitor
Power changes and the specific method of control polymerization inhibitor rate of release, polymerization inhibition effect period of supervision also only have 3 months.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation method of the inhibition coating for aromatic olefin monomers,
By changing coating material formulation, make coating that there is inhibition while anti-corrosion, and by changing the addition side of polymerization inhibitor
Method, solves the problem that coating adhesion declines after polymerization inhibitor adds in the prior art.
The preparation method of inhibition coating of the present invention for aromatic olefin monomers, comprises the following steps：
(1) under nitrogen protective condition, using EP828 types epoxy resin as raw material, ethers auxiliary agent is added, heating stirring is anti-
Should, it is standby that coating surface layer base-material is made；
(2) after carrying out heating stirring reaction according to the step described in step (1), cooling, polymerization inhibitor is added into system, is entered
Row insulation reaction, it is standby that coating bottom strata base-material is made；
(3) curing agent is added separately to be well mixed in above two base-material；
(4) aromatic olefin monomers reservoir walls are brushed by the way of layering is brushed, first brushing bottom base-material is formed
Primer coating, then brushing surface layer base-material form surface layer coating, and wherein primer coating be coating containing polymerization inhibitor, surface layer coating for without
Polymerization inhibitor coating.
In step (1), reaction temperature is 150~200 DEG C, and the reaction time be 1~5h, preferable reaction temperature for 160~
200 DEG C, the reaction time is 3~5h.
In step (2), the compound as polymerization inhibitor can be hydroxylamine compound such as dihydroxypropyl azanol (HPHA)；Benzene
Aminated compounds such as N, N '-diisobutyl p-phenylenediamine；Phenol compound such as hydroquinones (HQ), 2,3,5- trimethyls -4-
Nitrosophenol, p-tert-Butylcatechol (TBC), the tertiary amyl hydroquinones (DTBHQ) of 2,5- bis-, 2,6- dibutyl -4- first
Base phenol etc.；Quinones such as benzoquinones, tert-butyl group benzoquinones (TBBQ), benzoquinones imidodicarbonic diamide, 1,4-naphthoquinone；NO free radical class
Tetramethyl -4- hydroxy-piperdines the oxygen radical (628D) of compound such as 2,2,6,6-, above-mentioned polymerization inhibitor it is one or more of it is compound
It can be applied in the coating material of storage tank.Preferable polymerization inhibitor is hydroxylamine compound, NO free radical class compound and benzene
Phenolic compound, or the compound of two of which；It is preferred that the compound of dihydroxypropyl azanol and tert-butyl group benzoquinones.
Dihydroxypropyl azanol is compounded with tert-butyl group benzoquinones, and preferably proportioning is dihydroxypropyl azanol：Tert-butyl group benzoquinones
Mass ratio is 1:6~6:1.
In step (2), gained reactant is cooled to 50~90 DEG C, after adding polymerization inhibitor, continues 1~3h of insulation reaction, compared with
Good reaction temperature is 50~70 DEG C, 1~2h of reaction time.
The percentage by weight that polymerization inhibitor addition accounts for reaction-ure mixture in step (2) is 1~40%, and preferable polymerization inhibitor adds
Enter amount account for reaction-ure mixture percentage by weight be 1~30%, preferably account for reaction-ure mixture percentage by weight be 5~25%.
Polymerization inhibitor addition is more, duration length is inhibited under similarity condition, but polymerization inhibitor addition is too big, can also influence coating material
Adhesive force and service life.
In step (3), curing agent is mixed with base-material, and base-material is 6~8 with curing agent mixed proportion:1 (volume ratio),
It is stirred 0.2~1h of time.The coating material standing time prepared does not exceed 24 hours, completes to apply preferably in 12 hours
Brush.Preferable curing agent is thick slurry amine additives, the preferably warm and sunny thick slurry amine additives curing agent of foreign board.
Layering painting way described in step (4), inhibition coating are made up of primer coating and surface layer coating, primer coating
For the coating containing polymerization inhibitor, surface layer is the coating without polymerization inhibitor.Wherein, the thickness of primer coating is 10 μm~300 μm, preferably
Ground is 30~100 μm；The thickness of surface layer coating is 10 μm~400 μm, and preferably scope is 50 μm~300 μm, preferably 100 μm
~250 μm.Coating adhesion is better than 3 grades after brushing, and adhesive force series is the smaller the better.
After coated, after aromatic olefin monomers steam runs into wall condensation, the polymerization inhibitor just slowly diffusion in coating
Into lime set, reach the purpose of inhibition.It can be controlled by adjusting polymerization inhibitor addition and coating surface thickness in Coating base
The rate of release of polymerization inhibitor in coating, polymerization inhibitor rate of release is slower, and the inhibition cycle is longer, so as to play the effect inhibited for a long time
Fruit.
The rate of release for investigating polymerization inhibitor is carried out in the carbon steel storage tank of certain volume, and tank deck is concave.By certain
Proportioning and painting way apply brush applied coating in tank deck, and the aromatic olefin monomers of certain volume are housed in tank, it is small to fix one close to tank top
Measuring cup, to collect the lime set of fragrant alkene gaseous monomer.Fragrant alkene in tank is heated to certain temperature, periodic collection lime set, and
The coating situation of change of top cover is checked, analyzes level of inhibitor in lime set, polymerization inhibitor is investigated from the burst size in coating, determines it
Inhibit the cycle.
Change the surface thickness of polymerization inhibitor addition and tank deck coating, collect tank deck lime set, analysis at the same temperature
Level of inhibitor therein, it is found that the increase of polymerization inhibitor addition, surface layer is thicker, and polymerization inhibitor discharges slower, polymerization inhibition time
It is longer.
The aromatic olefin monomers that the present invention is directed to can refer to styrene, p-methylstyrene, o-methyl styrene, the tert-butyl group
Styrene, two fragrant alkene benzene, chlorostyrene, bromstyrol etc..
Compared with prior art, the invention has the advantages that：
The present invention is reacted by adding polymerization inhibitor during prepares coating base-material, is obtained with anti-corrosion and inhibition
The new coating material of performance, polymerization inhibitor addition is big, and coating adhesion is good, is grown, assigned using the rear coating inhibition duration
Coating material new polymerization inhibition performance；Inhibition coating use two layers of painting way, coating dosage is few, and adhesive force is good, can by
Prepare the economic benefits and social benefits measure that polymerization inhibitor addition is adjusted during base-material and surface thickness is adjusted in painting process, effectively control
The rate of release of polymerization inhibitor in coating, so as to reach the effect inhibited for a long time, the inhibition cycle can reach more than 10 years, fundamentally
Solves the polymerism during aromatic olefin monomers storage；Painting process in the present invention is simple, and inhibition coating is effectively being reduced
While monomer polymerization causes the product to lose, the product quality in storage tank is can guarantee that, polymer is eliminated and dissolves in product and cause
The contamination of products even whole underproof hidden danger of tank product, extends the maintenance clear tank cycle.
Embodiment
With reference to embodiment, the present invention is further illustrated, but it is not intended to limit the implementation of the present invention.
Embodiment 1~5：It is prepared by coating surface layer base-material
With agitator, reflux condenser 1L reactors in, add EP828 type epoxy resin 400g, glycidol
Ether auxiliary agent 100g, heat temperature raising under nitrogen environment, prepares coating surface layer base-material；Thickness slurry amine additives curing agent is added before brushing
Enter into prepared base-material and be stirred, wherein the mixed proportion 6 of base-material and thick slurry amine additives:1 (volume ratio), during stirring
Between 0.3h.Then above-mentioned epoxy resin coating is brushed on standard tinplate (50 × 100 × 0.2~0.3mm), coating layer thickness is about
100μm.Coating tests adhesive force after parching, differential responses conditional test results are as shown in table 1.
The coating surface layer base-material preparation condition of table 1
| Embodiment | Reaction temperature/DEG C | Reaction time/h | Coating adhesion |
| 1 | 150 | 5 | 3 grades |
| 2 | 160 | 3 | 2~3 grades |
| 3 | 170 | 3 | 2~3 grades |
| 4 | 180 | 2 | 2~3 grades |
| 5 | 200 | 1 | 3 grades |
As can be seen from Table 1, the coating material prepared as stated above can meet requirement.
Embodiment 6~16：Coating bottom strata base-material is prepared (prepared by inhibition Coating base)
After reaction terminates described in embodiment 3, be cooled to 50~90 DEG C, continue to stir, added into system it is a kind of or
Two kinds of compound polymerization inhibitors, 1~3h of insulation reaction, obtain the Coating base with different polymerization inhibition performances.Similarly, will before brushing
Thickness slurry amine additives curing agent, which is added in above-mentioned base-material, to be stirred, wherein the mixed proportion 8 of base-material and thick slurry amine additives:
1 (volume ratio), mixing time 1h.Then the brushing above-mentioned material on standard tinplate (50 × 100 × 0.2~0.3mm), apply
About 80 μm of thickness degree.Coating tests adhesive force after parching, as a result as shown in table 2：
Table 2 inhibits Coating base preparation condition
| Embodiment | Polymerization inhibitor species | Polymerization inhibitor addition | Reaction temperature | Reaction time | Coating adhesion |
| 6 | HPHA | 5 | 50 | 3 | 2 grades |
| 7 | HQ | 1 | 60 | 2 | 2 grades |
| 8 | TBC | 25 | 70 | 1 | 2 grades |
| 9 | DTBHQ | 30 | 80 | 1 | 2~3 grades |
| 10 | TBBQ | 40 | 90 | 1 | 3 grades |
| 11 | 628D | 35 | 60 | 2 | 2~3 grades |
| 12 | TBC+628D | 10 | 70 | 2 | 2 grades |
| 13 | TBBQ+HQ | 15 | 50 | 3 | 2 grades |
| 14 | TBBQ+HPHA | 5 | 60 | 1.5 | 2 grades |
| 15 | TBBQ+HPHA | 20 | 60 | 1.5 | 2 grades |
| 16 | TBBQ+HPHA | 25 | 60 | 1.5 | 2 grades |
Note：In table 2：TBC in embodiment 12:628D mass ratioes are 3:1；TBBQ in embodiment 13:HQ mass ratioes are 2:1；
TBBQ in embodiment 14,15:HPHA mass ratioes are 4:1；TBBQ in embodiment 16:HPHA mass ratioes are 1:2.
As shown in Table 2, inhibition coating is prepared according to the method described in the present invention, and coating adhesion is good, meets to use and wants
Ask.After above-mentioned coated plate is soaked into one week in styrene, coating is still intact, and no peeling, obscission occur.
Embodiment 17~20：Coating polymerization inhibition effect is inhibited to investigate
The brushwork epoxy resin paint on 5L styrene storage tank tank deck inwall, epoxy resin coating preparation method are as follows：In band
In the 1L reactors for having agitator, reflux condenser, EP828 type epoxy resin 500g, glycidol ether auxiliary agent 120g are added, is used
Nitrogen purges 10 minutes, opens stirring, is heated to 170 DEG C, after reacting 2h, is cooled to 60 DEG C, takes out about half reactant
It is stand-by.Then compound polymerization inhibitor TBBQ+HPHA is added into system, addition is answered for 27%, the TBBQ and HPHA of reaction volume
It is 3 with mass ratio:Insulation reaction 2h under the conditions of 1,60 DEG C, obtains the Coating base with polymerization inhibition performance.
The brushing styrene storage tank tank deck by the way of two layers of overcoating, wherein base-material are mixed with thick slurry amine additives curing agent
Composition and division in a proportion example 7:1 (volume ratio), is stirred time 1h.Brushed according to different bottom and surface thickness, bottom is containing inhibition
Agent, surface layer are free of polymerization inhibitor.
After the completion of brushing, under the conditions of 40 DEG C of storage temperature, periodic collection styrene lime set, analyze polymerization inhibitor therein and contain
Amount, the results are shown in Table 3, table 4.
Under 3 different bottoms of table and surface thickness in lime set level of inhibitor change
From table 3 it is observed that under conditions of polymerization inhibitor addition is certain, can be preferable by changing surface thickness
The rate of release of polymerization inhibitor in ground control coating, surface layer is thicker, and polymerization inhibition time is longer, produces a desired effect.
If not adding polymerization inhibitor in coating, polymer just occurs in tank deck under similarity condition, is adhered on inwall.
According to the overcoating mode and bottom of embodiment 19, surface thickness, change polymerization inhibitor addition, collect styrene and coagulate
Liquid, analyzes level of inhibitor therein, and experimental result is listed in Table 4 below.
Under the conditions of the different polymerization inhibitor additions of table 4 in lime set level of inhibitor change
It can be seen that after improving polymerization inhibitor addition, after 1 month, level of inhibitor all tends towards stability in lime set, can control
The rate of release of polymerization inhibitor, extend inhibition coating service life.
In terms of the tank top coating described in embodiment 19, the inhibition service life of coating is investigated.According to the inhibition of addition
Level of inhibitor in agent total amount and the lime set amount of collection, it may be determined that the burst size of polymerization inhibitor in coating.In storage temperature 40
Under the conditions of DEG C, the polymerization inhibitor rate of release change in the coating of embodiment 19 is listed in table 5.
The burst size change of polymerization inhibitor in the coating of table 5
As shown in Table 5, first month polymerization inhibitor burst size accounts for the 4.9% of total addition, the release of second month polymerization inhibitor
Amount discharges after accounting for the 6.5% of total addition substantially to be slowed down, and is monthly discharged with 0.4%~0.5% speed, is released after six months
High-volume burst size about 10.8% after about 8.4%, 1 year, by this estimation, sustainable more than 10 years of coating polymerization inhibition performance.Commercial Application
During, for the storage temperature of aromatic olefin monomers typically all below 15 DEG C, the lime set amount of storage tank inner roof wall will be less than the present embodiment,
Therefore under industrial condition of storage, polymerization inhibitor rate of release is slower in coating, and polymerization inhibition performance should last much longer.
Embodiment 25
On the basis of the inhibition coating production described in embodiment 19 and overcoating mode, epoxy coating is applied to 5L
Methyl styrene storage tank tank deck inwall on, wherein 60 μm of underlayer thickness, 200 μm of surface thickness.Polymerization inhibitor is made using TBC, added
Enter amount accounts for coating content 35%.Under the conditions of 40 DEG C of storage temperature, periodic collection methyl styrene lime set, level of inhibitor change
It is shown in Table 6.
The changes of contents of polymerization inhibitor in the methyl styrene lime set of table 6
It can be seen that inhibition coating is used for into methyl styrene, it can equally reach the purpose slowly discharged.This method can also be used for
The storage tank of other aromatic olefin monomers such as t-butyl styrene, chlorostyrene, two fragrant alkene benzene.
Claims (8)
1. the preparation method of a kind of inhibition coating for aromatic olefin monomers, it is characterised in that comprise the following steps：
（1）Under nitrogen protective condition, using EP828 types epoxy resin as raw material, ethers auxiliary agent is added, heat up stirring reaction, system
It is standby to obtain coating surface layer base-material；
（2）According to step（1）After described step carries out heating stirring reaction, cooling, polymerization inhibitor is added into system, is protected
Temperature reaction, it is standby to be made coating bottom strata base-material；
（3）Curing agent is added separately to be well mixed in above two base-material；
（4）Aromatic olefin monomers reservoir walls are brushed by the way of layering is brushed, first brushing bottom base-material forms bottom
Coating, then brushing surface layer base-material form surface layer coating, and wherein primer coating is coating containing polymerization inhibitor, and surface layer coating is without inhibition
Agent coating；
Step（1）Middle reaction temperature is 150~200 DEG C, and the reaction time is 1~5h；
Step（2）In be cooled to 50~90 DEG C, add polymerization inhibitor, carry out 1~3h of insulation reaction, polymerization inhibitor addition accounts for reactant
The percentage by weight of total amount is 1~40%.
2. the preparation method of the inhibition coating according to claim 1 for aromatic olefin monomers, it is characterised in that：Step
（1）Middle ethers auxiliary agent is glycidol ether.
3. the preparation method of the inhibition coating according to claim 1 for aromatic olefin monomers, it is characterised in that：Polymerization inhibitor
For the one or more in hydroxylamine compound, phenol compound, quinones or NO free radical class compound.
4. the preparation method of the inhibition coating according to claim 3 for aromatic olefin monomers, it is characterised in that：Azanol class
Compound is dihydroxypropyl azanol；Amino benzenes compounds are N, N '-diisobutyl p-phenylenediamine；Phenol compound is to benzene two
Phenol, 2,3,5- trimethyl -4- nitrosophenols, p-tert-Butylcatechol, the tertiary amyl hydroquinones of 2,5- bis- or the fourths of 2,6- bis-
One or more in base -4- methylphenols；Quinones is benzoquinones, tert-butyl group benzoquinones, benzoquinones imidodicarbonic diamide or Isosorbide-5-Nitrae-naphthalene
One or more in quinone；NO free radical class compound is 2,2,6,6- tetramethyl -4- hydroxy-piperdine oxygen radicals.
5. the preparation method of the inhibition coating according to claim 4 for aromatic olefin monomers, it is characterised in that：Polymerization inhibitor
For dihydroxypropyl azanol and the compound of tert-butyl group benzoquinones, both mass ratioes are 1:6~6:1.
6. the preparation method of the inhibition coating according to claim 1 for aromatic olefin monomers, it is characterised in that：Step
（3）In, the volume ratio of base-material and curing agent is 6~8:1,0.2~1h of time is stirred, curing agent is thick slurry amine additives.
7. the preparation method of the inhibition coating according to claim 1 for aromatic olefin monomers, it is characterised in that：Step
（4）The thickness of middle primer coating is 10 μm~300 μm, and the thickness of surface layer coating is 10 μm~400 μm.
8. the preparation method of the inhibition coating according to claim 1 for aromatic olefin monomers, it is characterised in that：Fragrant alkene
Monomer refers to styrene, p-methylstyrene, o-methyl styrene, t-butyl styrene, two fragrant alkene benzene, chlorostyrene, bromine
Styrene.
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| CN105837465A (en) * | 2016-03-29 | 2016-08-10 | 威海翔宇环保科技股份有限公司 | Synthesis of styrene polymerization inhibitor |
| CN107474682A (en) * | 2016-06-08 | 2017-12-15 | 中国石油化工股份有限公司 | The storage method of styrene monomer |
| CN108912944B (en) * | 2017-03-31 | 2020-11-17 | 中国石油化工股份有限公司 | Polymerization-inhibiting coating, preparation method thereof and application thereof in styrene monomer storage tank |
| CN107266284A (en) * | 2017-07-26 | 2017-10-20 | 徐文忠 | A kind of polymerization inhibitor and its preparation method and application |
| CN111318045B (en) * | 2018-12-14 | 2022-12-16 | 中国石油化工股份有限公司 | Extractive distillation column for isoprene separation and separation method |
| CN117024243B (en) * | 2023-08-21 | 2024-01-23 | 淄博润祥工贸有限公司 | N-isopropyl hydroxylamine used as styrene butadiene rubber inhibitor and preparation method thereof |
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