Background technology
Letex polymerization is produced styrene-butadiene rubber(SBR) and is included under the effect of redox initiator, use RA rosin acid and fatty acid soaps blending emulsifiers, oxygenant is that di-isopropylbenzene hydroperoxide, hydrogen peroxide pinane or hydrogen peroxide are to alkane in the Meng, sodium formaldehyde sulphoxylate and iron edta sodium salt are reductive agent, make divinyl and vinylbenzene carry out the low temperature emulsion polymerization.
Letex polymerization is produced the used terminator of styrene-butadiene rubber(SBR) and is generally contained dimethyl dithiocarbamate, dialkyl group azanol, Sodium Nitrite etc., dialkyl group azanol and dithiocar-bamate are in the sour environment of emulsion condensation process, easily form secondary amine, the amino-oxide (NOx) that exists in secondary amine and nitration reagent such as Sodium Nitrite (hereinafter to be referred as C), air reaction forms nitrosamine.
As far back as the eighties, permitted great synthetic rubber production company promptly begin one's study new polymerization terminator and vulcanization accelerator in the world, replace to form the Sodium dimethyldithiocarbamate 40min (being called for short SDD) and the diethyl hydroxylamine (DEHA) of secondary amine, to eliminate or to reduce to greatest extent the generation of nitrosamine.
Buna-(the Gerhard Horpol of Xiu Ersi company, Joachim Pangratz, US4965326) with the terminator of aromatic hydrocarbons hydroxyl dithionic acid as Raolical polymerizable, no nitrosamine preparation body produces in the products therefrom, and the add-on of terminator is 0.1~1 part in per hundred parts of polymkeric substance.
(Stjtske M.De Vries, EP437293 US5177164) then use sodium polysulphide as reaction terminating agent separately in the Shell Oil Co..In the typical polyreaction, used sodium polysulphide is Na
2S
4, its consumption is 0.02~0.5phm (parts by weight of per hundred parts of total monomer inlet amounies).Its shortcoming is the sodium polysulphide large usage quantity, and the sulphur in the prescription easily is deposited on the production line, generate hydrogen sulfide and etching apparatus, and hydrogen sulfide odor is also given very offending sensation.But the nitrosamine amount that generates during as terminator is few, and the termination effect of polyreaction is preferable.
(Richard Maestri US5384372) uses isopropylhydroxyla or its esters as terminator, and concrete kind has N-isopropylhydroxyla, acetate isopropylhydroxyla, hydrochloric acid isopropylhydroxyla and sulfuric acid isopropylhydroxyla in Goodyear Tire ﹠ Rubber Co.The terminator consumption is 0.05~0.2phm, and its adding method is the same with common terminator adding method, preferably it is formulated as the aqueous solution and joins in the polyreaction that reaches certain transformation efficiency.
(Piero Maestri, the poly-used terminator of butylbenzene device of breast US5504168) is acetate isopropylhydroxyla and sodium polysulphide in Italy ENI chemistry elastomerics company.It is said, use these two kinds of compounds to be terminator, neither can produce nitrosamine, also can not deposit down sulphur in the pipeline and produce corrosion, and significantly reduce the generation of hydrogen sulfide.The consumption of terminator acetate isopropylhydroxyla is 0.01~0.03phm, and the consumption of sodium polysulphide is 0.005~0.015phm.Two kinds of compounds are used in combination, and can reduce the consumption of terminator, and it is wherein a kind of that total consumption will be less than independent use.
(LOU Jianfeng, Buszta Thomas EP1083185) when using DEHA, add the nitrosamine inhibitor to Lou Jianfeng etc.
Summary of the invention
Technical problem to be solved by this invention provides a kind of compound and preparation method thereof, and this compound makes not contain nitroso compound in the finished product as the terminator of letex polymerization production styrene-butadiene rubber(SBR).
The invention provides a kind of monoalkyl or single aryl dithiocar-bamate, its structural formula is:
R-NHCS
2M
R is C in the formula
1Above alkyl or aryl, M is NH
4 +Or metal ion.
The preferred scheme of said structure formula is: R is C
1~C
5Alkyl or phenyl, phenmethyl, styroyl; Metal ion is K
+, Na
+
The preparation method of monoalkyl or single aryl dithiocar-bamate is with R-NH
2, CS
2, MOH is that raw material reacts generation under 0~70 ℃ temperature of reaction, with molar ratio computing, R-NH
2: CS
2: MOH=1~2: 1: 1~1.5.
In order to improve the transformation efficiency of reaction, R-NH
2, the excessive adding of MOH, preferred mol ratio is: R-NH
2: CS
2: MOH=1~1.5: 1: 1~1.3.
The preferred value of temperature of reaction is 0~50 ℃, and the reaction times was at least 3 hours.
The purposes of monoalkyl or single aryl dithiocar-bamate is to produce the reaction terminating agent of styrene-butadiene rubber(SBR) as letex polymerization.Both can use separately, also can replace dimethyl dithiocarbamate as stated in the Background Art.
Use no matter use separately or substitute, the consumption of monoalkyl or single aryl dithiocar-bamate is 0.02~1.0phm, preferred 0.02~0.8phm.
After adopting the present invention to make terminator, do not change the technology that styrene-butadiene rubber(SBR) is produced in existing letex polymerization.
Advantage of the present invention:
Can stably prepare the qualified styrene-butadiene rubber(SBR) of mooney viscosity, and make in the styrene-butadiene rubber(SBR) of preparation and do not contain nitroso compound.The technical indicator of monoalkyl or single aryl dithiocar-bamate is:
Terminator R-NHCS
2The M technical indicator
Project | Index |
Outward appearance | Light yellow or orange liquid |
Purity m/m% | ????≥10 |
Density (20 ℃) g/m
3 | ????1.025~1.055 |
Free alkali (NaOH meter) m/m% | ????0.05~0.5 |
Reducing power % | ????≥6.5 |
PH value | ????9.0~12.5 |
Embodiment
Further specify the present invention with comparative example in conjunction with the embodiments, but do not limit the scope of the invention.
Embodiment 1
In 3 liters of reaction flasks that have stirring, chuck, temperature indication or still, add CS
215 weight parts under agitation drip CH
3NH
26.5 weight part and 20%NaOH 45 weight parts, control reaction temperature is not higher than 40 ℃.React and made product in 3 hours.
The results are shown in table 1.
Embodiment 2
CH
3NH
26 weight parts and 20%NH
3H
2O 40 weight parts.All the other are with embodiment 1.
Embodiment 3
C
4H
9NH
262 weight parts and 40%KOH 110 weight parts, CS
225 weight parts.All the other are with embodiment 1.
Embodiment 4
CH
3NH
230 weight parts, 40%KOH 110 weight parts, all the other are with embodiment 1.
Embodiment 5
C
6H
5NH
225 weight parts and 10%NaOH 150 weight parts, CS
218 weight parts.All the other are with embodiment 1.
Comparative Examples 1
CH
3NHCH
312 weight parts, 10%NaOH 150 weight parts, CS
218 weight parts.All the other are with embodiment 1.Product is SDD (Sodium dimethyldithiocarbamate 40min).Contain nitroso compound in the styrene-butadiene rubber(SBR) of preparation.
The preparation condition of table 1 terminator and termination effect
| Proportioning (part) | Product | Nitroso compounds μ g/Kg in the rubber |
Embodiment 1 | CH
3N
H2?6.5
| ?CS
2?15
| ?20%NaOH ?45 | ?CH
3NHCS
2Na
| 0 |
Embodiment 2 | CH
3NH
26
| ?CS
2?15
| ?20%NH
3·H
2O ?40
| ?CH
3NHCS
2NH
4 | 0 |
Embodiment 3 | C
4H
9NH
2?62
| ?CS
2?25
| ?40%KOH ?110 | ?C
4H
9NHCS
2K
| 0 |
Embodiment 4 | CH
3NH
2?30
| ?CS
2?25
| ?40%KOH ?110 | ?CH
3NHCS
2K
| 0 |
Embodiment 5 | C
6H
5NH
2?25
| ?CS
2?18
| ?10%NaOH ?150 | ?C
6H
9NHCS
2Na
| 0 |
Comparative Examples 1 | CH
3NHCH
312
| ?CS
2?18
| ?10%NaOH ?150 | ?(CH
3)
2NCS
2Na
| 10 |
Below give an example for the technology of letex polymerization production styrene-butadiene rubber(SBR):
Single aryl dithiocarbamate salt in the following example is called for short D, oxammonium hydrochloride or oxammonium sulfate, is called for short E, sodium sulphite or hydrated sodium sulfide (Na
2S.9H
2O), be called for short S, Methyl disulfide, be called for short SDD, dialkyl group azanol, vehicle economy HA for formate.
The consumption of SDD or D is 0.02~1.0phm,
The consumption of E or DEHA is 0.005~0.5phm,
S or Sodium Nitrite add-on are 0.005~0.5phm.
Comparative Examples 2: 10 liters of polymeric kettles with having stirring, chuck, temperature, pressure indication make 1.3-divinyl and vinylbenzene carry out letex polymerization.Under nitrogen protection; in polymeric kettle, add vinylbenzene 32 weight parts; divinyl 68 weight parts; water 205 weight parts; each 2.5 weight part of fatty acid soaps and RA rosin acid; and logical cold water cooling in polymeric kettle; treat to add when the polymeric kettle temperature is reduced to 5 ℃ di-isopropylbenzene hydroperoxide (DIP); or hydrogen peroxide pinane (PHP) or hydrogen peroxide are to alkane in the Meng (PMHP) 0.04 weight part; sodium formaldehyde sulphoxylate (SFS) 0.05 weight part; iron edta sodium salt (EDTAFeNa) 0.05 weight part; reacted 8~12 hours down at 5 ℃; monomer conversion reaches at 62~75% o'clock; add terminator SDD 0.4phm; the consumption of DEHA is 0.15phm, Sodium Nitrite 0.08phm.The results are shown in table 3.Rubber performance is listed in table 4.
Embodiment 6
Add terminator D 0.36phm, the consumption of DEHA is 0.15phm, Sodium Nitrite 0.08phm.All the other are with Comparative Examples 2.
Embodiment 7
Terminator SDD 0.4phm, the consumption of DEHA are 0.15phm, S (sodium sulphite) 0.06phm.All the other are with Comparative Examples 2.
Embodiment 8
Terminator SDD 0.4phm, the consumption of E (oxammonium hydrochloride) is 0.12phm, S (sodium sulphite) 0.06phm.All the other are with Comparative Examples 2.
Embodiment 9
Only with terminator E (oxammonium hydrochloride), the consumption of E is 0.55phm, and all the other are with Comparative Examples 2.
Comparative Examples 3
Only with terminator SDD and DEHA, the consumption of SDD is 0.42phm, and the consumption of DEHA is 0.152phm, and all the other are with Comparative Examples 2.
Embodiment 10
Terminator D 0.36phm, E (oxammonium sulfate) 0.12phm, S (hydrated sodium sulfide) 0.04phm, all the other are with Comparative Examples 2.
Embodiment 11
Only use terminator E (oxammonium sulfate) and S (sodium sulphite), the consumption 0.50phm of E, the consumption 0.04phm of S, all the other are with Comparative Examples 2.
Embodiment 12
Adopt terminator D, consumption is 0.45phm, and all the other are with Comparative Examples 2.
Embodiment 13
Adopt terminator D, consumption is 0.40phm, the consumption 0.14phm of E (oxammonium hydrochloride), and all the other are with Comparative Examples 2.
Embodiment 14
Adopt terminator D, consumption is 0.40phm, the consumption 0.10phm of S (hydrated sodium sulfide), and all the other are with Comparative Examples 2.
Embodiment 15
Adopt terminator D, consumption is 0.36phm, the consumption 0.15phm of E (oxammonium hydrochloride), and the consumption 0.06phm of S (sodium sulphite), all the other are with Comparative Examples 2.
Embodiment 16
Adopt terminator D, consumption is 0.36phm, DEHA consumption 0.15phm, and the consumption 0.06phm of S (hydrated sodium sulfide), all the other are with Comparative Examples 2.
Table 3 polymeric reaction condition and termination effect
| Terminator consumption (phm) | Polymerisation conversion | Add terminator transformation efficiency % after 24 hours | Nitroso compounds μ g/Kg |
Comparative Examples 2 | ?SDD?0.4 | ?DEHA?0.15 | ?NaNO2?0.08 | ?70.32 | ?70.85 | ?10 |
Embodiment 6 | ?D???0.36 | ?DEHA?0.15 | ?NaNO2?0.08 | ?70.45 | ?70.93 | ?0 |
Embodiment 7 | ?SDD?0.4 | ?DEHA?0.15 | ?S?0.06 | ?69.54 | ?69.68 | ?0 |
Embodiment 8 | ?SDD?0.4 | ?E??0.12 | ?S?0.06 | ?69.55 | ?69.88 | ?0 |
Embodiment 9 | | ?E??0.50 | | ?70.05 | ?71.23 | ?0 |
Comparative Examples 3 | ?SDD?0.42 | ?DEHA?0.15 | | ?73.12 | ?73.43 | ?0 |
Embodiment 10 | ?D?0.36 | ?E?0.10 | ?S?0.04 | ?63.65 | ?64.01 | ?0 |
Embodiment 11 | | ?E?0.50 | ?S?0.04 | ?66.23 | ?66.73 | ?0 |
Embodiment 12 | ?D?0.45 | | | ?71.25 | ?71.48 | ?0 |
Embodiment 13 | ?D?0.40 | ?E?0.14 | | ?70.38 | ?70.65 | ?0 |
Embodiment 14 | ?D?0.40 | | ?S?0.10 | ?69.72 | ?70.02 | ?0 |
Embodiment 15 | ?D?0.36 | ?E?0.15 | ?S?0.06 | ?71.68 | ?71.93 | ?0 |
Embodiment 16 | ?D?0.36 | ?DEHA?0.15 | ?S?0.06 | ?70.42 | ?70.65 | ?0 |
The different terminator prescriptions of table 4 are to the influence of rubber physical mechanical property
| ?ML(1+4) ?100℃ | 300% stretches (MPa) surely | Tensile strength (MPa) | Elongation % |
?25’ | ?35’ | ?50’ |
Comparative Examples 2 | ?46.5 | ?12.3 | ?15.2 | ?17.0 | ?24.5 | ?471 |
Embodiment 6 | ?46.5 | ?12.1 | ?14.1 | ?16.4 | ?24.1 | ?488 |
Embodiment 7 | ?47 | ?11.8 | ?14.9 | ?16.4 | ?24.1 | ?474 |
Embodiment 8 | ?46.5 | ?11.6 | ?14.3 | ?16.1 | ?23.6 | ?478 |
Embodiment 9 | ?46.0 | ?13.1 | ?14.2 | ?16.5 | ?24.0 | ?470 |
Comparative Examples 3 | ?46.5 | ?12.8 | ?14.4 | ?16.8 | ?24.3 | ?492 |
Embodiment 10 | ?47.0 | ?12.4 | ?14.8 | ?16.6 | ?24.6 | ?475 |
Embodiment 11 | ?46.5 | ?12.5 | ?14.9 | ?16.9 | ?24.3 | ?490 |
Embodiment 12 | ?47.5 | ?11.9 | ?14.6 | ?16.8 | ?24.3 | ?485 |
Embodiment 13 | ?47.0 | ?12.1 | ?14.8 | ?16.9 | ?24.1 | ?472 |
Embodiment 14 | ?46.5 | ?12.3 | ?14.9 | ?16.7 | ?24.7 | ?470 |
Embodiment 15 | ?47.0 | ?12.0 | ?14.5 | ?16.5 | ?24.5 | ?475 |
Embodiment 16 | ?47.0 | ?12.4 | ?15.0 | ?16.7 | ?24.6 | ?482 |
Below enumerate the embodiment of several terminators again:
Embodiment 17:
According to embodiment 1, C
2H
5NH
215 weight parts, 10%NaOH 130 weight parts, CS
220 weight parts, temperature of reaction 50C.
Embodiment 18:
According to embodiment 1, C
5H
11NH
233 weight parts, 40%KOH 40 weight parts, CS
220 weight parts, 60 ℃ of temperature of reaction.
Embodiment 19:
According to embodiment 1, R-CH
2In R be phenmethyl 34 weight parts, 40%KOH 35 weight parts, CS
216 weight parts, 0 ℃ of temperature of reaction.
Embodiment 20:
According to embodiment 1, R-CH
2In R be styroyl 45 weight parts, 40%KOH 50 weight parts, CS
225 weight parts.