CN1429847A - Preparation method of emulsion polymerized rubber without nitroso compound - Google Patents
Preparation method of emulsion polymerized rubber without nitroso compound Download PDFInfo
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- CN1429847A CN1429847A CN 02148335 CN02148335A CN1429847A CN 1429847 A CN1429847 A CN 1429847A CN 02148335 CN02148335 CN 02148335 CN 02148335 A CN02148335 A CN 02148335A CN 1429847 A CN1429847 A CN 1429847A
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- sodium nitrite
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Abstract
A process for preparing the emulsion polymerization rubber (butadiene styrene rubber) not containing nitroso compound features that the components D, E and S are used as the reaction terminating agents to replace original SDD, DEHA and sodium nitrite in a defined manner. The said D is the monoalkyl or monoaryl bithioaminoformate. The said E is the hydroxyamine hydrochloride (or sulfate). The said S is sodium sulfite or hydrated sodium sulfide.
Description
Technical field
The invention belongs to the Polymer Synthesizing field, relate to a kind of preparation method of emulsion(polymerized)rubber, promptly when emulsion polymerization stops, adopt the material that does not contain nitroso compound or do not contain nitroso-group preparation body, the preparation emulsion(polymerized)rubber.
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.Add reaction terminating agent in the outlet line of polyreaction end still, to stop polyreaction, carry out the divinyl flash distillation then, latex enters the vinylbenzene degassing tower again and outgases, and carries out aftertreatment then and forms finished product glue.
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.
Equally carry out divinyl rubber that emulsion(polymerized)rubber that the low temperature letex polymerization obtains such as polymerizing butadiene obtain, comprise by the copolymer rubber paracril of divinyl and vinyl cyanide, the chloroprene rubber that the chloroprene polymerization obtains etc. by conjugated diene.The terminator that polyreaction adopted is identical with above-mentioned situation.
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 (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 foot sodium polysulphide large usage quantity, 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.
The Ceng Genyi of Mitsubishi chemical company helps (spy opens 2000-248007) and uses specific dithiocar-bamate R
1R
2NCS
2M makes terminator, and addition should use with Sodium Nitrite during use at 0.02～1.0phm.R wherein
1R
2Expression C
5Above alkyl or phenyl, M represents Na, K or quarternary ammonium salt.Ceng Genyi helps (spy opens 2000-248008) and also finds to use monoalkyl dithiocar-bamate R-NH-CS
2M has the effect identical with above-mentioned terminator as terminator, and addition is at 0.02～1.0phm, and R represents C
1～C
3Alkyl and its Sodium Nitrite or the saltpetre add-on used simultaneously be 0.005～0.5phm.
(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 is in the preparation process of emulsion(polymerized)rubber, select specific reaction terminating agent for use, make the emulsion(polymerized)rubber of preparation not contain nitroso compound, and can stably prepare the qualified polyrubber of mooney viscosity, the present invention is particularly useful for the preparation of styrene-butadiene rubber(SBR).
The preparation method who does not contain the emulsion(polymerized)rubber of nitroso compound of the present invention is characterized in that the reaction terminating agent of emulsion polymerization is selected following component:
Single aryl or monoalkyl dithiocarbamate salt are called for short D, oxammonium hydrochloride or oxammonium sulfate, are called for short E, sodium sulphite or hydrated sodium sulfide (Na
2S.9H
2O), be called for short S, dithiocarbamate salt, be called for short SDD, dialkyl group azanol, vehicle economy HA, Sodium Nitrite (potassium), and form different reaction terminating agents in the following manner:
A kind of, two or three composition among D, E, the S, but do not comprise independent S component;
One or both compositions in D and DEHA, the Sodium Nitrite (potassium), but do not comprise the composition of monoalkyl dithiocarbamate salt and Sodium Nitrite (potassium);
One or both compositions in E and SDD, the Sodium Nitrite (potassium);
One or both compositions among S and SDD, the DEHA;
D, E and Sodium Nitrite (potassium) are formed;
D, S and DEHA form;
SDD and E, S form;
More than forming SDD and Sodium Nitrite (potassium) can not use simultaneously.The preferred Sodium Nitrite of described Sodium Nitrite (potassium).
Wherein the structural formula of D is expressed as:
R-NHCS
2M
R is aryl or alkyl in the formula.
Principal feature of the present invention is to select for use D, E, S component as reaction terminating agent, the terminator of being made up of SDD, DEHA, Sodium Nitrite (potassium) that replaces that prior art generally uses.D replaces SDD during replacement, and E replaces DEHA, and S replaces Sodium Nitrite (potassium).The main effect of three kinds of components of terminator is different, and the effect of SDD or D is to stop polyreaction; The main effect of DEHA or E is the end polygalacturonase inhibitor, suppresses the formation of popcorn polymer in the gas phase when the degassing, but the same effect that also has the termination polyreaction with D of independent E; S or Sodium Nitrite (potassium) can be eliminated intrasystem dissolved oxygen, and be many with S or Sodium Nitrite (potassium) in the sealing water.S or Sodium Nitrite (potassium) independent in actual production can not use separately, preferably by three kinds not the component of same-action use simultaneously, wherein two kinds also can be used, but the cleaning cycle of degassing tower will shorten.Therefore, after the present invention selects D, E, S component for use, can form terminator by wherein a kind of (not comprising independent S component), two or three component, also can have synergy between them simultaneously by a kind of, the known component of two or three corresponding replacement wherein.Its adding method is the same with common terminator adding method, and other processing condition of emulsion polymerization are constant.
Reaction terminating agent of the present invention from the above mentioned preferably is made up of three kinds of components, preferably is made up of D, E and three kinds of components of S, not only makes not contain nitroso compound in the emulsion(polymerized)rubber, does not also contain nitroso-group preparation body simultaneously.
No matter how to select component between SDD, DEHA, Sodium Nitrite (potassium), D, E, the S, the consumption when each component is participated in compatibility is basic identical with prior art, is respectively:
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 (potassium) add-on is 0.005～0.5phm.During a kind of in selecting D, E separately for use, its amount can be bigger in above-mentioned scope.
By last description, characteristics of the present invention have been found the terminator of two kinds of products of D, E as emulsion(polymerized)rubber (especially styrene-butadiene rubber(SBR)) polyreaction especially.
The general formula of described single aryl or monoalkyl dithiocarbamate salt is expressed as: R-NHCS
2R is C in the M formula
1Above alkyl or phenyl or
N=1～6, 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
+C wherein
3～C
5Alkyl mainly be meant n-propyl, normal-butyl or n-pentyl respectively.Substituting group on the phenyl ring is preferably straight chain group.
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.
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 |
Advantage of the present invention:
Make in the polyrubber of preparation not contain nitroso compound, and can stably prepare the qualified polyrubber of mooney viscosity.The present invention is particularly useful for the preparation of styrene-butadiene rubber(SBR).
Embodiment
Producing styrene-butadiene rubber(SBR) with letex polymerization is example.D component among embodiment 1, embodiment 5, the embodiment 7～11 is: R-NHCS
2M, R are preferably methyl, ethyl, n-propyl, normal-butyl, n-pentyl, phenyl, phenmethyl or styroyl, and M is NH
4 +Or K
+, Na
+
Comparative Examples 1:
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 32 parts of vinylbenzene; 68 parts of divinyl; 205 parts in water; each 2.5 parts of fatty acid soaps and RA rosin acids; 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 0.04 part in alkane in the Meng (PMHP); 0.05 part of sodium formaldehyde sulphoxylate (SFS); 0.05 part of iron edta sodium salt (EDTAFeNa); reacted 8～12 hours down at 5 ℃, monomer conversion reaches at 62～75% o'clock, adds terminator SDD 0.4phm; the consumption of DEHA is 0.15phm, Sodium Nitrite 0.08phm.The results are shown in table 1.Rubber performance is listed in table 2.
Embodiment 1
Add terminator D 0.36phm, the consumption of DEHA is 0.15phm, Sodium Nitrite 0.08phm.All the other are with Comparative Examples 1.
Embodiment 2
Terminator SDD 0.4phm, the consumption of DEHA are 0.15phm, S (sodium sulphite) 0.06phm.All the other are with Comparative Examples 1.
Embodiment 3
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 1.
Embodiment 4
Only with terminator E (oxammonium hydrochloride), the consumption of E is 0.55phm, and all the other are with Comparative Examples 1.
Comparative Examples 2
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 1.
Embodiment 5
Terminator D 0.36phm, E (oxammonium sulfate) 0.12phm, S (hydrated sodium sulfide) 0.04phm, all the other are with Comparative Examples 1.
Embodiment 6
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 1.
Embodiment 7
Adopt terminator D, consumption is 0.45phm, and all the other are with Comparative Examples 1.
Embodiment 8
Adopt terminator D, consumption is 0.40phm, the consumption 0.14phm of E (oxammonium hydrochloride), and all the other are with Comparative Examples 1.
Embodiment 9
Adopt terminator D, consumption is 0.40phm, the consumption 0.10phm of S (hydrated sodium sulfide), and all the other are with Comparative Examples 1.
Embodiment 10
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 1.
Embodiment 11
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 1.
Table 1 polymeric reaction condition and termination effect
| Terminator consumption (phm) | Polymerisation conversion | Add the transformation efficiency % of terminator after 0.5 hour | Add the transformation efficiency % of terminator after 10 hours | Add terminator transformation efficiency % after 24 hours | Nitroso compounds μ g/Kg | Mechanical stability of latex % | |||
| Comparative Examples 1 | ??SDD ??0.4 | ?DEHA ?0.15 | ?NaNO2 ?0.08 | ?70.32 | ?71.25 | ?70.95 | ?70.85 | ?10 | ?2.52 |
| Embodiment 1 | ??D ??0.36 | ?DEHA ?0.15 | ?NaNO2 ?0.08 | ?70.45 | ?70.62 | ?70.83 | ?70.93 | ?0 | ?2.48 |
| Embodiment 2 | ??SDD ??0.4 | ?DEHA ?0.15 | ?S ?0.06 | ?69.54 | ?70.02 | ?69.95 | ?69.68 | ?0 | ?2.38 |
| Embodiment 3 | ??SDD ??0.4 | ?E ?0.12 | ?S ?0.06 | ?69.55 | ?69.73 | ?69.85 | ?69.88 | ?0 | ?2.40 |
| Embodiment 4 | ?E ?0.50 | ?70.05 | ?71.52 | ?71.33 | ?71.23 | ?0 | ?2.42 | ||
| Comparative Examples 2 | ??SDD ??0.42 | ?DEHA ?0.15 | ?73.12 | ?73.55 | ?73.21 | ?73.43 | ?0 | ?2.45 | |
| Embodiment 5 | ??D ??0.36 | ?E ?0.10 | ?S ?0.04 | ?63.65 | ?64.02 | ?64.48 | ?64.01 | ?0 | ?2.47 |
| Embodiment 6 | ?E ?0.50 | ?S ?0.04 | ?66.23 | ?66.53 | ?66.65 | ?66.73 | ?0 | ?2.40 | |
| Embodiment 7 | ??D ??0.45 | ?71.25 | ?71.95 | ?71.72 | ?71.48 | ?0 | ?2.55 | ||
| Embodiment 8 | ??D ??0.40 | ?E ?0.14 | ?70.38 | ?70.45 | ?70.60 | ?70.65 | ?0 | ?2.48 | |
| Embodiment 9 | ??D ??0.40 | ?S ?0.10 | ?69.72 | ?70.21 | ?70.15 | ?70.02 | ?0 | ?2.46 | |
| Embodiment 10 | ??D ??0.36 | ?E ?0.15 | ?S ?0.06 | ?71.68 | ?71.85 | ?71.80 | ?71.93 | ?0 | ?2.40 |
| Embodiment 11 | ??D ??0.36 | ?DEHA ?0.15 | ?S ?0.06 | ?70.42 | ?70.45 | ?70.52 | ?70.65 | ?0 | ?2.35 |
From table the result as can be seen, terminator of the present invention has reached the termination effect of prior art terminator, and product is not influenced its performance, clearly embodies easilier from following table 2.
The different terminator prescriptions of table 2 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 1 | ?46.5 | ?12.3 | ?15.2 | ?17.0 | ?24.5 | ?471 |
| Embodiment 1 | ?46.5 | ?12.1 | ?14.1 | ?16.4 | ?24.1 | ?488 |
| Embodiment 2 | ?47 | ?11.8 | ?14.9 | ?16.4 | ?24.1 | ?474 |
| Embodiment 3 | ?46.5 | ?11.6 | ?14.3 | ?16.1 | ?23.6 | ?478 |
| Embodiment 4 | ?46.0 | ?13.1 | ?14.2 | ?16.5 | ?24.0 | ?470 |
| Comparative Examples 2 | ?46.5 | ?12.8 | ?14.4 | ?16.8 | ?24.3 | ?492 |
| Embodiment 5 | ?47.0 | ?12.4 | ?14.8 | ?16.6 | ?24.6 | ?475 |
| Embodiment 6 | ?46.5 | ?12.5 | ?14.9 | ?16.9 | ?24.3 | ?490 |
| Embodiment 7 | ?47.5 | ?11.9 | ?14.6 | ?16.8 | ?24.3 | ?485 |
| Embodiment 8 | ?47.0 | ?12.1 | ?14.8 | ?16.9 | ?24.1 | ?472 |
| Embodiment 9 | ?46.5 | ?12.3 | ?14.9 | ?16.7 | ?24.7 | ?470 |
| Embodiment 10 | ?47.0 | ?12.0 | ?14.5 | ?16.5 | ?24.5 | ?475 |
| Embodiment 11 | ?47.0 | ?12.4 | ?15.0 | ?16.7 | ?24.6 | ?482 |
Below enumerate several preparation embodiment of monoalkyl or single aryl dithiocar-bamate, do not limit the present invention:
Embodiment 12
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.
Embodiment 13
CH
3NH
26 weight parts and 20%NH
3H
2O 40 weight parts.All the other are with embodiment 12.
Embodiment 14
C
4H
9NH
262 weight parts and 40%KOH 110 weight parts, CS
225 weight parts.All the other are with embodiment 12.
Embodiment 15
CH
3NH
230 weight parts, 40%KOH 110 weight parts, all the other are with embodiment 12.
Embodiment 16
C
6H
5NH
225 weight parts and 10% NaOH, 150 weight parts, CS
218 weight parts.All the other are with embodiment 12.
Embodiment 17:
According to embodiment 12, C
2H
5NH
215 weight parts, 10%NaOH 130 weight parts, CS
220 weight parts, 50 ℃ of temperature of reaction.
Embodiment 18:
According to embodiment 12, 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 12, 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 12, R-CH
2In R be styroyl 45 weight parts, 40%KOH 50 weight parts, CS
225 weight parts.
Claims (9)
1, the preparation method who does not contain the emulsion(polymerized)rubber of nitroso compound is characterized in that the reaction terminating agent of emulsion polymerization is selected following component:
Single aryl or monoalkyl dithiocarbamate salt are called for short D, oxammonium hydrochloride or oxammonium sulfate, are called for short E, sodium sulphite or hydrated sodium sulfide, be called for short S, dithiocarbamate salt, be called for short SDD, dialkyl group azanol, vehicle economy HA, Sodium Nitrite, reaction terminating agent is formed in the following manner:
A kind of, two or three composition among D, E, the S;
One or both compositions in D and DEHA, the Sodium Nitrite (potassium), but do not comprise the composition of monoalkyl dithiocarbamate salt and Sodium Nitrite (potassium);
One or both compositions in E and SDD, the Sodium Nitrite (potassium);
One or both compositions among S and SDD, the DEHA;
D, E and Sodium Nitrite (potassium) are formed;
D, S and DEHA form;
SDD and E, S form;
More than forming SDD and Sodium Nitrite (potassium) can not use simultaneously, does not comprise independent S component;
Wherein the structural formula of D is expressed as:
R-NHCS
2M
R is aryl or alkyl in the formula, and M is NH
4 +Or metal ion.
2, method according to claim 1 is characterized in that reaction terminating agent is made up of D, E and three kinds of components of S.
3, method according to claim 1 and 2 is characterized in that the consumption of each component is respectively:
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.
4, method according to claim 1, the aryl that it is characterized in that described single aryl dithiocarbamate salt be selected from phenyl or
N=1～6, M is NH
4 +Or K or Na.
5, method according to claim 4, the aryl that it is characterized in that single aryl dithiocarbamate salt is phenyl, phenmethyl or styroyl.
6, method according to claim 1, the alkyl R that it is characterized in that described monoalkyl dithiocarbamate salt is C
1～C
5Alkyl.
7, method according to claim 6 is characterized in that described C
1～C
5Alkyl be methyl, ethyl, n-propyl, normal-butyl or n-pentyl.
8, method according to claim 1 is characterized in that M is K
+Or Na
+
9, method according to claim 1 is characterized in that it being the emulsion polymerization that is undertaken by divinyl and vinylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02148335 CN1217960C (en) | 2001-12-31 | 2002-11-06 | Preparation method of emulsion polymerized rubber without nitroso compound |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01142879 | 2001-12-31 | ||
| CN011428791 | 2001-12-31 | ||
| CN01142879.1 | 2001-12-31 | ||
| CN 02148335 CN1217960C (en) | 2001-12-31 | 2002-11-06 | Preparation method of emulsion polymerized rubber without nitroso compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1429847A true CN1429847A (en) | 2003-07-16 |
| CN1217960C CN1217960C (en) | 2005-09-07 |
Family
ID=25740639
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|---|---|---|---|
| CN 02148335 Expired - Fee Related CN1217960C (en) | 2001-12-31 | 2002-11-06 | Preparation method of emulsion polymerized rubber without nitroso compound |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467656A (en) * | 2013-09-16 | 2013-12-25 | 吉林市盛之源化工助剂有限责任公司 | Environment-friendly type terminating agent for styrene butadiene rubber emulsion polymerization and preparation method thereof |
| CN105985489A (en) * | 2015-02-15 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method of nitrosamine-free emulsion-polymerized integrated rubber |
| CN110922529A (en) * | 2019-11-21 | 2020-03-27 | 淄博奥固特科技有限公司 | Pyridine styrene butadiene rubber latex and preparation method thereof |
| CN112830996A (en) * | 2019-11-25 | 2021-05-25 | 中国石油天然气股份有限公司 | Composition for terminating emulsion polymerization and use thereof |
-
2002
- 2002-11-06 CN CN 02148335 patent/CN1217960C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467656A (en) * | 2013-09-16 | 2013-12-25 | 吉林市盛之源化工助剂有限责任公司 | Environment-friendly type terminating agent for styrene butadiene rubber emulsion polymerization and preparation method thereof |
| CN105985489A (en) * | 2015-02-15 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method of nitrosamine-free emulsion-polymerized integrated rubber |
| CN110922529A (en) * | 2019-11-21 | 2020-03-27 | 淄博奥固特科技有限公司 | Pyridine styrene butadiene rubber latex and preparation method thereof |
| CN112830996A (en) * | 2019-11-25 | 2021-05-25 | 中国石油天然气股份有限公司 | Composition for terminating emulsion polymerization and use thereof |
| CN112830996B (en) * | 2019-11-25 | 2022-11-01 | 中国石油天然气股份有限公司 | Composition for terminating emulsion polymerization and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1217960C (en) | 2005-09-07 |
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