CN102336844A - Method for chemically removing residual monomers in rubber latex - Google Patents
Method for chemically removing residual monomers in rubber latex Download PDFInfo
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- CN102336844A CN102336844A CN201010231458XA CN201010231458A CN102336844A CN 102336844 A CN102336844 A CN 102336844A CN 201010231458X A CN201010231458X A CN 201010231458XA CN 201010231458 A CN201010231458 A CN 201010231458A CN 102336844 A CN102336844 A CN 102336844A
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- rubber latex
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- 229920000126 latex Polymers 0.000 title claims abstract description 62
- 239000000178 monomer Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000004816 latex Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- 239000007858 starting material Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 8
- 229920000459 Nitrile rubber Polymers 0.000 claims description 7
- 229920013649 Paracril Polymers 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 150000004972 metal peroxides Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 238000007872 degassing Methods 0.000 abstract description 6
- 229920001971 elastomer Polymers 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000005060 rubber Substances 0.000 abstract description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 4
- 235000013305 food Nutrition 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 229920006174 synthetic rubber latex Polymers 0.000 abstract 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 24
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 21
- 239000012071 phase Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 208000031639 Chromosome Deletion Diseases 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- MLGZWBPQUONOQV-UHFFFAOYSA-M potassium (Z)-octadec-9-enoate hydrate Chemical compound [OH-].[K+].C(CCCCCCCC=C/CCCCCCCC)(=O)O MLGZWBPQUONOQV-UHFFFAOYSA-M 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000019600 saltiness Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A method for chemically removing residual monomers in rubber latex is characterized in that in the process of obtaining the rubber latex by emulsion polymerization of monomers, when the monomer conversion rate reaches more than 85%, heating is carried out, the reaction temperature is increased, a water-soluble initiator is supplemented under the nitrogen charging pressure of 0.02 MPa-0.04 MPa, and the addition amount of an initiator solution is preferably 0.1-2 parts by weight based on 100 parts by weight of dry rubber of the latex; the reaction time is 1-3 hours. The rubber prepared by the method for removing the residual monomers in the latex has low impurity content, short degassing time and high production efficiency. Can be suitable for the synthetic rubber latex with strong adhesiveness, such as gel, no gel, high Mooney viscosity, low Mooney viscosity, polar group and the like. The obtained product can be used for medical gloves, condoms, coating films for food packaging and other products.
Description
Technical field
The present invention relates to the chemical removal method of residual monomer in a kind of rubber latex; In more detail, be a kind of method to the employing of the residual monomer in rubber latex chemical reaction, reach the purpose that removes; Mainly be difficult to remove with the sl. sol. partial monosomy of water; It is reduced to below the 50ppm, it is applied in the daily lifes such as health care, food and packing thereof, rather than only is applied in industrial use.
Background technology
What adopt about the method that removes of the residual monomer in the rubber latex is most at present, is that physics or physical-chemical method reach the purpose that makes its reduction.
Physical method:
The airtight method of physics is meant and under agitation condition, in airtight container, adds latex. adopts and improves temperature, reduce the vacuum tightness method residual monomer is broken away from from emulsion; After the gas phase separation, the method that condensation liquid phase again reclaims is intermittently preparation but use this method; Degassing efficiency is low, and energy consumption is high.
Physical-chemical method:
Physical-chemical method is meant and adopts the isolating method of freezing to separate volatile high boiling point monomers that the back recycling of purifying utilizes not volatile monomeric wetting ability to adopt solution to put forward dense method again and is implemented in utilization; Use this method can continuous production, recycle, but complex procedures; Equipment is many; Energy consumption is high, and is prone to form superoxide, and production safety hidden danger is many.
All there be the problem of the cleaning degassing with equipment in above method, and nonproductive consumption rate is bigger on raw material, PT, plant factor.
CN00800974.0 removes the apparatus and method of unreacted monomer from the polymer latex Ruzhong, disclose the apparatus and method that remove the unreacted monomer that polymer latex Ruzhong with high foam properties contains efficiently, and wherein device comprises cylindrical tower; One or more column plates wherein have a lot of apertures on the column plate, column plate is installed on the vertical direction in tower; Partition and overflow wall are arranged on each column plate, and it is its bottom surface that one or more cells, column plate are arranged on one or more column plates; There is the latex relief outlet at the cell place that forms on the minimum column plate; The cell place that at least one higher column plate, forms has a latex intake at least, and degassing mouth is arranged in the position that is higher than the latex intake, and downtake pipe is arranged; Latex is through the column plate of downtake pipe below top column plate flows to; The steam intake is arranged below the minimum column plate, and the height of cell is 3 to 300 times of overflow wall height, and the sectional area of tower is 50 to 1000 times of the total area that pass the aperture of column plate; Wherein method is used said apparatus.
CN 95102919.3 " removes the method and the tower of residual monomer ", CN97181495.3 " removes the method and apparatus of residual monomer " and all discloses a kind of method and apparatus that residual monomer prevents SE degraded and its downgrade simultaneously of from the slurry that contains SE, removing.
Also do not have at present a kind of method to adopt the form of chain chemical reaction, residual monomer removing or utilizing in the realization letex polymerization.
Summary of the invention
The object of the present invention is to provide the chemical removal method that removes unreacted monomer residual in the rubber latex that a kind of energy consumption is low, production efficiency is high.
The method of residual monomer chemical removal in a kind of rubber latex is characterized in that monomer obtains in the process of rubber latex through letex polymerization, when monomer conversion reaches 85% when above; Filling under the nitrogen pressure of 0.02MPa～0.04MPa; Adding water soluble starter, is 100 parts in the latex dry glue quality, and the initiator solution addition is preferably 0.1～2 part; Heating; Improve 3～25 ℃ of temperature of reaction, react and removed monomer residual in the rubber latex in 1～3 hour, the order of wherein fill nitrogen, adding water soluble starter and heating is adjustable.
Because the initiator of adding among the present invention can be decomposed to form the free radical activity point fast; Take nitrogen pressure to reduce the distribution of residual monomer in gas phase simultaneously; Monomeric molecule is shifted to liquid phase by gas phase; Reach and make the major part of residual monomer be dissolved in aqueous phase, the molecule agglomeration that makes residual monomer reaches the purpose that removes residual monomer thereby accomplished residual monomer in 1～3 hour through reaction in the polyreaction of aqueous portion on the molecular chain that the polymerization in early stage forms.
Characteristics of the present invention are to adopt a spot of water miscible initiator; The partial monosomy that makes polymerization reaction late stage not have to transform continues the very low level of agglomeration reaction to residual quantity, and the yield of product is improved, and the suitability of product is strengthened; Because its staple is N, H, O; And decompose the back agglomeration on molecular chain, noresidue in product does not have secondary pollution; Also reduced because reclaim the related production cost of residual monomer.
The present invention is applicable to the technology of batchwise polymerization; The technology mode that also can be used for successive polymerization; The technology of batchwise polymerization can be added water miscible initiator through equilibration tube on the polymerization reactor or jar, adopts volume pump to add initiator at continuous polymerization technique.
Rubber latex among the present invention is a synthetic latex, has particularly used the emulsion polymerization latex of negatively charged ion or nonionic emulsifying agent, the independent polymkeric substance-content of polybutadiene rubber latex of conjugated diolefine hydrocarbon compound that polymerization makes like conventional emulsion etc.; The binary of vinyl compounds such as conjugated diolefine hydrocarbon compound and vinylbenzene, vinyl cyanide, vinylformic acid, methylacrylic acid or terpolymer-styrene butadiene rubber latex, paracril latex, carboxy nitrile rubber latex, carboxylic styrene-butadiene rubber latex etc.
The used water soluble starter of the present invention can be in hydrogen peroxide and metal peroxides, the ammoniacal liquor etc. one or more.The reason that adopts hydrogen peroxide and metal peroxides thereof, ammoniacal liquor is that it decomposes soon, and decomposition induction time is short, and efficiency of initiation is high, decomposes the back noresidue.
These initiators--hydrogen peroxide and metal peroxides thereof, ammoniacal liquor etc. use with aqueous solution form, are 100 parts of weight in the dried glue weight of latex, and addition is preferably 0.1～2 part; Concentration is the general concentration of this technical field, is preferably 2%～25%.Initiator amount or (with) concentration is not enough, the latex residual monomer is difficult for removing, if consumption is too big, though can remove residual monomer, can increase initiator amount, increases product cost.The present invention does not limit the pH value of rubber latex.
The letex polymerization that is applicable to various temperature of reaction types of the present invention, modal have low temperature letex polymerization, a high temperature letex polymerization.In the present invention, the temperature of reaction of low temperature letex polymerization is controlled at 5 ± 1 ℃ or 8 ± 1 ℃ usually, and the temperature of reaction of high temperature letex polymerization is controlled at 30～47 ℃ usually.In the present invention, according to the difference of reaction type, the initiator for reaction temperature of adding among the present invention is higher than the polymerization temperature in early stage respectively, and low temperature emulsion polymerization temperature preferably improves 4～8 ℃, preferably improves 13～20 ℃ than high temperature emulsion polymerization temperature.
The present invention does not get rid of the application of other temperature condition controls yet.
The present invention does not get rid of the use of other auxiliary agent that is suitable for causing simultaneously.Because be that the present invention is the continuation reaction of minute quantity unreacted monomer, and early stage, reacting weight was smaller relatively, polymericular weight changes little, so the performance of the finished product rubber or rubber item does not change.
The order of fill nitrogen among the present invention, adding water soluble starter and heating is adjustable, and putting upside down of order do not have too big influence to the present invention.
Residual monomer in the rubber latex after removal methods of the present invention removes, better than the removal effect of physics or physical-chemical method, and also energy consumption is low, less equipment investment, and production efficiency is high, and product is more wide on environmental protection and food product pack etc. are used.
The rubber foreign matter content that the method for using latex residual monomer of the present invention to remove makes is few, and the degassing time is short, and production efficiency is high.Can be adapted to contain gel, gel-free, high Mooney viscosity, low mooney viscosity and have the strong viton latex of cementability such as polar group.
Embodiment
Below explain that with embodiment but the present invention is not limited to these embodiment.Only if outside specializing among the present invention, " part ", " % " all refer to mass percent.
Rubber latexs among the embodiment etc. are said as follows:
1. paracril latex (to call NBR in the following text)
The nitrile rubber that CNPC's Lanzhou Petrochemical is produced.
2. styrene-butadiene latex (to call SBR in the following text)
Styrene butadiene rubber latex SBR-1500, XSBR, SBR-1712 that CNPC's Lanzhou Petrochemical is produced.
Embodiment 1
The PNBR special-purpose latex
At 3M
3225 kilograms of emulsifying agent waters of latex formulations amount in the polymeric kettle (potassium stearate and potassium oleate water miscible liquid) and reaction monomers oil phase (380 liters of 800 liters of divinyl and vinyl cyanide) add 80 kilograms of persulfate aqueous solutions under vacuum, reacted 12～15 hours down at 40 ℃; Reach at 92%～96% o'clock at monomer conversion, the time add 2.6 kilograms superoxol (concentration 30%) again, in reactor drum, fill nitrogen 0.2MPa; Be increased to 65 ℃ of reactions 2～3 hours; Monomer conversion is reached more than 99.5%, be cooled to 25 ℃ of following dischargings after, cohesion back is detected; Bound acrylonitrile>=38.5%, mooney viscosity
Gel 55%, tensile strength>=24.5MPa, the free acrylonitrile content of tensile yield>=400%, 300% stress at definite elongation>=12MPa are below 50ppm, and divinyl is residual to be zero.
Embodiment 2
Flood special-purpose nitrile rubber
At 21M
3The emulsifying agent water of latex formulations amount (sodium lauryl sulphate water miscible liquid) 2.59M in the polymeric kettle
3With reaction monomers oil phase (divinyl 4.3M
3, vinyl cyanide 3.6M
3, vinylformic acid 1.5M
3), under vacuum, add 96 kilograms of the ammonium persulfate aqueous solution, reacted 8～12 hours down at 30 ℃; Reach at 92%～96% o'clock at monomer conversion, add 75.9 kilograms ammonia soln (concentration 33%) again, in reactor drum, fill more than the nitrogen 0.2MPa; Be increased to 45 ℃ the reaction 2～3 hours, monomer conversion is reached more than 99.5%, be cooled to 25 ℃ of following dischargings after; Detect free acrylonitrile content below 50ppm, divinyl is residual to be zero.
Main physical index:
Total solids>=45%, vinyl cyanide binding capacity>=30%, acrylonitrile content≤50ppm dissociates in viscosity≤50mPas Ph7.5～9
Embodiment 3
Carboxy nitrile rubber latex
. at 21M
3The emulsifying agent water of latex formulations amount (sodium lauryl sulphate water miscible liquid 2.85M in the polymeric kettle
3) and reaction monomers oil phase (divinyl 5.5M
3, vinyl cyanide 3.2M
3, methylacrylic acid 1.26M
3), under vacuum, add 96 kilograms of persulfate aqueous solutions, reacted 8～12 hours down at 40 ℃, reach at 92%～96% o'clock at monomer conversion; Add 29.6 kilograms superoxol (concentration 30%) again, in reactor drum, fill more than the nitrogen 0.2MPa, be increased to 55 ℃ of reactions 2～3 hours; Monomer conversion is reached more than 99.5%, be cooled to 25 ℃ of following dischargings after, detect free acrylonitrile content below 50ppm; Divinyl is residual to be zero, bound acrylonitrile>=32.5%, tensile strength>=26.8MPa; Tensile yield>=280%, 100% stress at definite elongation,>=9.3MPa.
Embodiment 4
The carpet special styrene-butadiene rubber latex
At 12M
3Emulsifying agent water of latex formulations amount in the polymeric kettle (760 kilograms of disproportionated rosin potassium soap liquid and 30 kilograms of copperas solutions, 40 kilograms of Diao Bai piece solution, 35 kilograms of Klorvess Liquids) and reaction monomers oil phase (divinyl 3.75M
3, vinylbenzene 2.86M
3, molecular weight regulator 0.8M
3), under vacuum, add 30 kilograms of the di-isopropylbenzene hydroperoxide aqueous solution, reacted 8～12 hours down at 5 ℃; Reach 95% when above at monomer conversion, add 28.7 kilograms superoxol (concentration 30%) again, in reactor drum, fill more than the nitrogen 0.2MPa; Be increased to 12 ℃ of reactions 2～3 hours, monomer conversion is reached more than 99.5%, after reaction finishes discharging; Detect free styrene content below 10ppm, divinyl is residual to be zero.
Embodiment 5
The N32 paracril
At 3M
3155 kilograms of emulsifying agent waters of latex formulations amount (X 2073 water miscible liquid) and reaction monomers oil phase in the polymeric kettle (296 liters of 805 liters of divinyl and vinyl cyanide) add 1 kilogram of the aqueous solution of di-isopropylbenzene hydroperoxide (solid content 3%) under vacuum, reacted 12～15 hours down at 8 ℃; Reach at 87%～89% o'clock at monomer conversion, the latex solid content is added 8.6 kilograms superoxol (concentration 30%) again 27 ± 0.3% when above; In reactor drum, fill more than the nitrogen 0.2MPa; Be increased to 12 ℃ of reactions 2～3 hours, the residual monomer transformation efficiency reached more than 99.8%, after the discharging; Mooney viscosity is detected in the cohesion back
Gel≤2%, bound acrylonitrile>=32.5%, free acrylonitrile content are below 20ppm, and divinyl is residual to be zero, tensile strength>=17.6MPa, tensile yield>=650%, 100% stress at definite elongation,>=6.3MPa.
Comparative Examples 1: flood special-purpose nitrile rubber (identical) with embodiment 2 conditions
At 21M
3The emulsifying agent water of latex formulations amount (sodium lauryl sulphate water miscible liquid) 2.59M in the polymeric kettle
3With reaction monomers oil phase (divinyl 4.3M
3, vinyl cyanide 3.6M
3, vinylformic acid 1.5M
3), under vacuum, add 96 kilograms of the aqueous solution of ammonium persulfate (solid content 3%), reacted 8～12 hours down at 30 ℃; Reach at 92%～96% o'clock at monomer conversion, latex is sent into the flash distillation operation, improve temperature through adopting; Reduce the vacuum tightness method residual monomer is broken away from from emulsion, after the gas phase separation, the method that condensation liquid phase again reclaims; After being cooled to 25 ℃ of following dischargings, detect free acrylonitrile content more than 1500ppm, divinyl is residual to be zero.
Main physical index: total solids>=45%, vinyl cyanide binding capacity>=30%, viscosity≤50mPas, pH 7.5～9 free acrylonitrile content＞350ppm
Employed latex, perhaps the cohesion after rubber, its leading indicator be latex rubbers content more than 35%, moisture content is below 65%, saltiness is below 0.5%.
Can find out that from embodiment, Comparative Examples according to the identical condition of embodiment, if only carry out the conventional vacuum flashing degassing, can not reach the object of the invention, free vinyl cyanide is between 1000～4000PPM.Same product; Adopt different degas methods; End-use has very big difference, and free acrylonitrile content is low can be used for goods such as filming of medical gloves, condom, food product pack, and free acrylonitrile content is high can only be used for goods such as common water-proof gloves.
Claims (5)
1. the method for residual monomer chemical removal in the rubber latex is characterized in that monomer obtains in the process of rubber latex through letex polymerization, when monomer conversion reaches 85% when above; Filling under the nitrogen pressure of 0.02MPa～0.04MPa; Adding water soluble starter, is 100 parts in the latex dry glue quality, and the initiator solution addition is preferably 0.1～2 part; Heating; Improve 3～25 ℃ of temperature of reaction, react and removed monomer residual in the rubber latex in 1～3 hour, the order of wherein fill nitrogen, adding water soluble starter and heating is adjustable.
2. method according to claim 1 is characterized in that rubber latex is selected from a kind of in content of polybutadiene rubber latex, styrene butadiene rubber latex, paracril latex, carboxy nitrile rubber latex, the carboxylic styrene-butadiene rubber latex.
3. method according to claim 1 is characterized in that water soluble starter is selected from one or more in hydrogen peroxide and metal peroxides thereof, the ammoniacal liquor.
4. method according to claim 1 when it is characterized in that letex polymerization is the low temperature letex polymerization, is added water soluble starter and is reacted, and needs heating, improves 4～8 ℃ of temperature of reaction.
5. method according to claim 1 when it is characterized in that letex polymerization is the high temperature letex polymerization, is added water soluble starter and is reacted, and needs heating, improves 13～20 ℃ of temperature of reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010231458 CN102336844B (en) | 2010-07-14 | 2010-07-14 | Method for chemically removing residual monomers in rubber latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010231458 CN102336844B (en) | 2010-07-14 | 2010-07-14 | Method for chemically removing residual monomers in rubber latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102336844A true CN102336844A (en) | 2012-02-01 |
| CN102336844B CN102336844B (en) | 2013-05-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 201010231458 Active CN102336844B (en) | 2010-07-14 | 2010-07-14 | Method for chemically removing residual monomers in rubber latex |
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| CN103450400A (en) * | 2012-06-01 | 2013-12-18 | 中国石油天然气股份有限公司 | Method for preparing carboxyl nitrile rubber by emulsion polymerization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944525A (en) * | 2005-10-04 | 2007-04-11 | Lg化学株式会社 | Method for preparing graft rubber latex having low residual monomer content |
| CN1982346A (en) * | 2005-12-16 | 2007-06-20 | 中国石油天然气股份有限公司 | Preparation method of maleimide resin emulsion |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1944525A (en) * | 2005-10-04 | 2007-04-11 | Lg化学株式会社 | Method for preparing graft rubber latex having low residual monomer content |
| CN1982346A (en) * | 2005-12-16 | 2007-06-20 | 中国石油天然气股份有限公司 | Preparation method of maleimide resin emulsion |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450400A (en) * | 2012-06-01 | 2013-12-18 | 中国石油天然气股份有限公司 | Method for preparing carboxyl nitrile rubber by emulsion polymerization |
| CN103450400B (en) * | 2012-06-01 | 2015-07-29 | 中国石油天然气股份有限公司 | Method for preparing carboxyl nitrile rubber by emulsion polymerization |
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