CN103288984A - Method for polymerizing isoprene rubber by utilizing isoprene waterborne emulsion - Google Patents
Method for polymerizing isoprene rubber by utilizing isoprene waterborne emulsion Download PDFInfo
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Abstract
The invention relates to a method for polymerizing isoprene rubber by utilizing isoprene waterborne emulsion. The isoprene rubber is prepared by coagulating, filtering, washing and drying degassed polyisoprene emulsion. The prepared isoprene gloves and related thin latex products are high in strength, high in extension rate, good in handfeel and anallergic to a human body, and can meet the requirements of different purposes.
Description
The present invention is 200910047806.5 for the Chinese invention patent application number, and the applying date is on March 19th, 2009, and denomination of invention is divided an application for " a kind of polyisoprene aqueous emulsion and be used for preparing the method for gloves and related products ".
Technical field:
The present invention relates to the method that a kind of polyisoprene aqueous emulsion prepares gloves and related products, specifically is that isoprene is obtained methods of polyisoprene emulsion by letex polymerization, then this methods of polyisoprene emulsion is used for preparing the method for gloves and related products.Belong to polymer chemistry, Polymer Physics, colloid chemistry, surface and interface chemistry, rubber physics and chemical field.
Background technology:
In the last few years, the synthetic latex development was very fast, and its main products has styrene-butadiene latex, polychloroprene latex, nitrile rubber, acrylate latex etc.Synthetic latex adopts the method for emulsion polymerization manufacturing usually, and water is cooked medium, has represented the developing direction of being changed by solvent-borne type product hydrotropisms product now, has been widely used in fields such as rubber, coating, tackiness agent.
Isoprene is a kind of important unsaturated and conjugated diolefin, mainly is used as the monomer of synthetic polyisoprenes rubber, and the preparation isoprene has that olefine aldehydr is synthetic, produces C in iso-pentane and dehydrogenation of isoamylene, the ethene refining in the industry
5Production methods such as cut separation, acetylenic ketone method, wherein C
5The development of cut partition method is very fast.Industrial isoprene monomer mainly is to prepare polyisoprene by solution catalyzing or ionic polymerization, is used for substituting natural rubber.Polyisoprene also can be prepared into emulsion, uses as latex product.
The preparation method of current methods of polyisoprene emulsion has two kinds: a kind of is to adopt outer emulsion process, it namely is medium with the organic solvent, adopt methods such as anionoid polymerization, polycoordination synthetic along 1,4 one polyisoprene solution, again with polyisoprene solution and water, an amount of emulsifying agent through high-speed stirring emulsification, remove and concentrate behind the solvent and get.Be polyisoprene latex with the preparation of this class methods as isobutylene-isoprene latex (isoprene-isobutene rubber latex), isoprene rubber latex, isoprene one acrylonitrile latex etc.
CN 1324874A discloses the method that a kind of acquisition has the polyisoprene rubber of high-cis 1,4 linkage content, and it is by polymerization and getting in the organic hydrocarbon solvent of inertia such as the organophosphate of monomer isoprene, rare earth metal, aluminum alkyls.
CN 85102250B discloses a kind of isoprene prepares polyisoprene rubber by mass polymerization under the rare earth catalyst effect method.
US Patent No. 3285869 discloses a kind of preparation method of methods of polyisoprene emulsion, namely obtains polyisoprene solution with Ziegler-Nata catalyzer or lithium catalyst by solution polymerization, disperses the back desolventizing with emulsifier solution emulsification then.
US Patent No. 3971746 discloses a kind of methods of polyisoprene emulsion of carboxylation, and it is to introduce 0.03%～20% carboxyl when solution polymerization, has improved the stability after the emulsification.
The another kind of employing is the conventional emulsion polymerization technique, is medium with water, formed through radical copolymerization by isoprene and other unsaturated vinyl monomer.
WO03/080722A1 discloses a kind of conjugated diene copolymer emulsion that can be used for dip forming, and the conjugated diene of wherein mentioning comprises 1,3 divinyl and isoprene.Isoprene by 30%～90%, 0.1%～20% unsaturated carboxylic acid, other unsaturated monomer copolymerization of 0～69.9%, the copolymer emulsion that makes can satisfy the requirement of dip forming, the gloves physical and mechanical properties of dip forming is good, can satisfy the needs of different purposes.
US Patent No. 687876682 discloses a kind of copolymer emulsion of dip forming, and the monomer of wherein mentioning comprises isoprene.Concrete enforcement is that the copolymer emulsion that makes can be used for flooding the gloves moulding by 60%～81% divinyl, 2%～3.5% unsaturated carboxylic acid, the alkylene unsaturated nitrile copolymerization of 17-35%.
The methods of polyisoprene emulsion high comprehensive performance that above-mentioned first method makes, isoprene compound with regular structure height, but it uses a large amount of organic solvents in production process down, not only has problem of environmental pollution, and organic solvent removes, to reclaim technology loaded down with trivial details, causes cost to raise.Second method is introduced vinyl cyanide, vinylformic acid isopolarity monomer and isoprene copolymer usually, reaches the purpose that improves emulsion intensity and stability.But because comonomer is water-soluble, the difference of reactive behavior, polyreaction is difficult to control, branchign of molecule, gel degree height, and the latex product performance prepares not as first method.Still there is not at present ripe polyisoprene copolymer emulsion commercialization.
Natural rubber latex gloves high comprehensive performance, but that life-time service causes easily is allergic.The allergic problem that these synthetic latex goods such as neoprene, butyronitrile, butylbenzene do not exist protein to cause, and oil resistant and chemical resistance are good, oxytolerant and ozonize, hyposmosis, penetration-resistant can be better than the natural rubber latex goods, and feel is the same with the natural rubber latex goods.Wherein neoprene and the industrialization of nitrile rubber goods, but the irritating smells of the recycling of polychloroprene latex goods and nitrile rubber and goods thereof etc. have influenced applying of they again.
Summary of the invention:
Technical problem first aspect to be solved by this invention provides a kind of preparation method of polyisoprene aqueous emulsion.This method by the reasonable cooperation of emulsifying agent, the optimization of reaction process control, obtains stable polyisoprene water latex through free-radical emulsion polymerization at normal temperatures and pressures when isoprene polymerization.Prepare the control of emulsion technological process in this way easily, constant product quality, physical and mechanical properties is good behind the emulsion film forming, can satisfy multi-purpose needs.
Technical problem second aspect to be solved by this invention provides the method that above-mentioned polyisoprene aqueous emulsion is used for preparing gloves and related products.
Preparation method as the polyisoprene aqueous emulsion of first aspect present invention, be to be monomer with the isoprene, be emulsification system with emulsifying agent, dispersion agent, adopt redox initiation system, under normal pressure and initiator initiation, obtain stable polyisoprene rubber emulsion through free-radical emulsion polymerization; It is characterized in that the mixed oil phase of described isoprene monomer and initiator adopts segmentation dropping mode to drip with the reductive agent in the redox initiation system together.
In the present invention, described segmentation dropping mode is for being divided into three sections droppings.Wherein first section isoprene monomer and the mixed oil phase of initiator, reductive agent dripping quantity are respectively the 5wt-15wt% of total mass separately; Second section isoprene monomer and the mixed oil phase of initiator, reductive agent dripping quantity are respectively the 10wt-20wt% of total mass separately, and the 3rd section isoprene monomer and the mixed oil phase of initiator, reductive agent dripping quantity are respectively the 65wt-85wt% of total mass separately.
Because the purity of isoprene is bigger to the rate of polymerization influence, therefore, in the preparation method of polyisoprene rubber emulsion of the present invention, the purity of isoprene monomer will reach more than 98%.
Initiator of the present invention is selected superoxide for use, and consumption is 0.02～0.08wt% of isoprene monomer consumption.
Described superoxide adopts a kind of or both mixing in acyl peroxide class, the hydroperoxide kind.Described acyl peroxide class is one or more the mixing in dibenzoyl peroxide amine, lauroyl peroxide amine, the decanoyl peroxide amine.Be preferably dibenzoyl peroxide amine (BPO).
Described hydroperoxide kind is a kind of in hydrogen peroxide, pinane hydrogen peroxide, tertbutyl peroxide, hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide, hydrogen peroxide tri-isopropyl benzene, t-butyl hydroperoxide isopropyl benzene, the hydrogen peroxide chloro diisopropylbenzene(DIPB) or both and both above mixing.Be preferably tertbutyl peroxide, di-isopropylbenzene hydroperoxide.Be preferably tertbutyl peroxide.
Emulsifying agent of the present invention is a kind of in anionic emulsifier, the nonionic emulsifier or is two kinds blending emulsifiers.
The present invention preferentially selects the anionic emulsifier with better emulsifying capacity for use, and described anionic emulsifier includes but not limited to: alkyl-sulphate, alkylsulfonate, alkylbenzene sulfonate, a kind of in the hard soap.
Described alkyl-sulphate is preferably sodium lauryl sulphate.
Described alkylsulfonate is preferably a kind of in sodium laurylsulfonate and the succsinic acid alkyl ester sodium sulfonate.
Described alkylbenzene sulfonate is preferably Sodium dodecylbenzene sulfonate.
Described hard soap is preferably sodium oleate, potassium oleate, a kind of in the nilox resin acid potash soap.
Described nonionic emulsifier includes but not limited to the alkylphenol polyoxyethylene.
The consumption of described anionic emulsifier is 2～12wt% of isoprene monomer total amount, and preferred consumption is 4-10wt%.
The blending emulsifiers of anionic emulsifier of the present invention and nonionic emulsifying agent, it makes up composite weight ratio is 9: 1-1: 9.Preferably than being 5: 1～1: 5.
The consumption of described blending emulsifiers is the 4-15wt% of isoprene monomer total amount, and preferred consumption is 4-10wt%.
The adding of dispersion agent of the present invention can make polymerization process more steady, the transformation efficiency height, and emulsion-stabilizing, gel is few, and polymerization efficiency improves.Described dispersion agent is selected condensation formaldehyde naphthalene sulfonic acid salt for use, Dispersant MF, dispersion agent NF or the dispersion agent N that described condensation formaldehyde naphthalene sulfonic acid salt is commercial grade or the mixed dispersant of their two or more formations.
Described dispersant dosage is 0.05～1wt% of isoprene monomer total amount, and preferred consumption is 0.1～0.8wt%.
Reductive agent consumption in the redox initiation system that the present invention adopts is with selecting for use kind different, but general consumption is the 0.22-2.6wt% of isoprene monomer total amount, and preferred consumption is 0.22-1.3wt%.
Described reductive agent is one or both and the two or more mixing in sodium bisulfite, sodium formaldehyde sulfoxylate, Sulfothiorine, V-Brite B, ferrous sulfate, iron protochloride, the xitix.
In the preparation method of polyisoprene aqueous emulsion of the present invention, can also select the molecular weight of molecular weight regulator control polyisoprene for use.The consumption of described molecular weight regulator is monomer total amount 0.05-0.8wt%, and preferred consumption is 0.1-0.5wt%.
Above-mentioned molecular weight regulator be just-DDM dodecyl mercaptan, just-14 carbon mercaptan, just-16 a kind of or two kinds and the two or more mixing in carbon mercaptan, uncle-DDM dodecyl mercaptan, uncle-14 carbon mercaptan, the uncle-16 carbon mercaptan.Preferably just-DDM dodecyl mercaptan, uncle-DDM dodecyl mercaptan.
Tank reactor is adopted in polyisoprene aqueous emulsion polymerization of the present invention, carries out under normal pressure; According to the temperature of reaction difference, be divided into two kinds of hot polymerization reaction and cold poly-reactions: wherein the hot polymerization temperature of reaction is 20～32 ℃, and total reaction time is between 25～40 hours; When reaction conversion ratio reaches 97.5% when above, add terminator, anti-aging agent makes reaction terminating; Behind the reaction terminating, polyisoprene latex is sent into degassing still, remove unreacted monomer through flash distillation, gas.
The terminator that above-mentioned polyreaction adopts is common compound with terminating free-radical polymerisation processes ability, a kind of in quinhydrones, Resorcinol, p-ten.-butylcatechol, MEHQ, diethanolamine, the Sodium dimethyldithiocarbamate 40min.Be preferably diethanolamine, Sodium dimethyldithiocarbamate 40min.The consumption of terminator is the 0.05-0.5wt% of isoprene monomer total amount, and preferred consumption is 0.1-0.3wt%.
The anti-aging agent that above-mentioned polyreaction adopts is a kind of in phenols, amine, sulfurous esters, the thioesters class anti-aging agent, and these all are applicable to emulsion of the present invention.Be preferably phenolic type antioxidant, described phenolic type antioxidant is antioxidant 264, antioxidant 2246, anti-aging agent 246, a kind of in antioxidant SP, the antioxidant d.The consumption of anti-aging agent is the 0.2-4wt% of monomer total amount, and preferred consumption is 0.3-2wt%.
It is to be formed through free-radical emulsion polymerization at normal temperatures and pressures by isoprene that the present invention adopts polyisoprene aqueous emulsion, wherein isoprene, initiator, reductive agent adopt segmentation to drip and increase the consumption of initiator and reductive agent, have improved the turnover ratio (rising to 97.5% by original 78%) of polymerization.Whole emulsion polymerization process is steady, and emulsion-stabilizing, gel are separated out few, the polymerization efficiency height.Whole process of preparation is a greenization production process.
Be used for preparing the method for gloves and relevant slim emulsion products as the polyisoprene aqueous emulsion of second aspect present invention, be will preparation polyisoprene water latex, after prevulcanized, make emgloves and relevant slim product with dip forming technology.
Dip forming technology of the present invention is to adopt the ion deposition gelatinizing process, and concrete steps are as follows:
1. mould cleans, and dries under 60～100 ℃ of conditions, and drying time is 0.5～5 minute;
2. soak peptizer, dry peptizer under 80～120 ℃ of conditions, drying time is 0.5～8 minute;
3. soak emulsion, under 60～100 ℃ of conditions, dry emulsion; Drying time is 0.5～5 minute;
4. leaching under 50～70 ℃ of conditions, crimping is handled;
5. crosslinked: carry out crosslinkedly under 80～120 ℃ of conditions, crosslinking time is 1～10 minute;
6. the demoulding;
7. wash with 50～80 ℃ of hot water, leaching obtains gloves and relevant slim emulsion products with aftertreatment.
Prepared polyisoprene emgloves and related products performance satisfy multi-level multiduty requirement, are easy to the demoulding, can realize the production of industrialization streamline.
Described prevulcanized is with the sulphur of particle diameter 100-500 nanometer and the aqueous dispersions of zinc oxide, joins in polyisoprene water latex or the synthetic latex, is heated to 40 ℃-60 ℃ then, insulated and stirred 1-2 hour; Again at normal temperatures, leave standstill 24-48 hour.Through after leaving standstill, emulsion is by slaking fully, and performance is more stable, is fit to the slim emulsion products of preparation, is the emgloves of 0.03-0.10mm as thickness.
In above-mentioned prevulcanized step, sulfur consumption is the 0.5-3wt% of quality of the emulsion, and zinc oxide dosage is the 0.5-5wt% of quality of the emulsion.
In above-mentioned prevulcanized step, described zinc oxide is partly replaced with vulcanization accelerator BZ, and wherein the consumption of vulcanization accelerator BZ is the 0.5-3wt% of quality of the emulsion, and zinc oxide dosage is the 0-5wt% of quality of the emulsion.
In the above-mentioned prevulcanized step, the preparation method of the aqueous dispersions of sulphur and vulcanization accelerator is mixed with water solution system with sulphur and zinc oxide or zinc oxide and vulcanization accelerator, and ball milling can obtain the aqueous dispersions of 500mg/h more than 72 hours then.
It mainly is that prevulcanized for emulsion provides the sulphur source that the effect of sulphur is selected in prevulcanized of the present invention for use, vulcanization accelerator such as zinc oxide play the sulfuration of activation sulphur, improving the wet gel strength at initial stage in gloves and the relevant slim emulsion products preparation process, thereby the emgloves that is conducive to obtain thinner thickness reaches the slim emulsion products (for example thickness is the emgloves of 0.03mm) of being correlated with.Reduce owing to the transparency of gloves and relevant slim emulsion products can increase along with the consumption of zinc oxide, so the present invention substitutes partial oxidation zinc with vulcanization accelerator, not only can promote the state of vulcanization of sulphur, but also can improve the gloves transparency significantly.
Prevulcanized of the present invention roughly can be experienced following four-stage: 1, the vulcanizing ingredient particle bumps by pedesis and latex particle in emulsion, forms several aggregation of particles bodies; 2, the small molecules of vulcanizing ingredient particle enters the inside of latex particle by diffusion and charge force; 3, small molecules meeting and the latex particle generation chemical crosslink reaction of a small amount of vulcanizing ingredient, the reticulated structure of formation covalent linkage; 4, new vulcanizing ingredient small molecules constantly spreads in latex particle, enters latex particle inside, produces new crosslinking reaction, and constantly repeats above-mentioned 2 and 3 process.
Because the activity of vulcanizing ingredient is more than low under the curing temperature under the room temperature, though still can make rubber molecule that interlinkage slowly takes place, and constantly because the outside of latex particle is constantly pushed inside to, but dissolving and the diffusion of Synergist S-421 95 small molecules in latex particle is main, and trends towards evenly along with the prolongation of storage period.
Therefore, the pre-vulcanization process of emulsion is the synthesis result of chemical action and physical action, and it has shortened the sulfuration process of latex to a great extent, makes colloidal property become with stable, thereby is conducive to next step processing treatment.
Adopt peptizer to carry out gelling in the ion deposition gelling step of the present invention.Used peptizer is the solution that high valent cationic type salt and auxiliary agent are formed, and metallic cation salt is calcium, zinc and aluminum ions hydrochloride or nitrate.
Owing to the described gloves that adopted technique scheme, the present invention to obtain and the thickness 0.03-0.50 millimeter of relevant slim emulsion products, the tensile strength of film is greater than 14MPa, and unit elongation is greater than 700%.With the polyisoprene gloves of the present invention's preparation, production process environmental protection, product performance are good, can be applicable to fields such as health care, electronic industry, science and techniques of defence and daily life.
As the polymerization synthetic polyisoprene of a second aspect of the present invention be by the methods of polyisoprene emulsion after the degassing through cohesion, filter, washing, dry and get, specifically comprise following steps:
(1) add flocculation agent in methods of polyisoprene emulsion, stable methods of polyisoprene emulsion is the unstability cohesion under the flocculation agent effect, generates the slurries that contain the rubber blob of viscose;
(2) filter, blob of viscose is separated from slurries;
(3) washing: blob of viscose is changed in the washing bath, wash with water;
(4) filter: blob of viscose is separated from the slurries of washing;
(5) blob of viscose dewater, drying.
Flocculation agent of the present invention is selected a kind of in mineral acid, metal-salt, the polymeric flocculant for use.
Described mineral acid is selected a kind of in hydrochloric acid, sulfuric acid, the nitric acid for use, is preferably sulfuric acid.
Described metal-salt is a kind of in 1 valency, divalent, the 3 valency metal-salts.Described 1 valency metal-salt is Na
+Salt, divalent metal-salt are Mg
2+, Ca
2+, Zn
2+Salt, 3 valency metal-salts are Al
3+Salt.Described Na
+Salt is NaCl; Described Mg
2+Salt is MgCl
2, MgSO
4Described Ca
2+Salt is CaCl
2, Ca (NO
3)
2Described Zn
2+Salt is Zn (NO
3)
2Described Al
3+Salt is AlCl
3, Al
2(SO
4)
3The preferred MgSO of described metal-salt
4, CaCl
2, Al
2(SO
4)
3
Described polymeric flocculant is polyacrylamide.
In preferred embodiment of the present invention, flocculation agent selects excellent CaCl
2With the combination of sulfuric acid, wherein CaCl
2As main flocculation agent, its consumption is 8～40wt% of emulsion total amount, generally is made into weight concentration and is 5～30% the aqueous solution and use, and preferably is made into weight concentration and is 10～20% the aqueous solution and use; Sulfuric acid is used for regulating the pH of slurries as coagulant aids, and pH controls 5～8, preferably controls 5.5～7.
In above-mentioned steps (2), slurries and newborn polyisoprene rubber blob of viscose are sent into the rinse bath or the service sink that have whipping appts then by vibratory screening apparatus or vibrating bed filtering separation.
In above-mentioned steps (3), blob of viscose is admitted to the rinse bath or the service sink that have whipping appts and washs, to remove soluble impurities such as a large amount of flocculation agent, emulsifying agent.
In above-mentioned steps (4), the slurries of washing and blob of viscose are by vibratory screening apparatus or vibrating bed filtering separation.
Contain a large amount of moisture content owing to filter the blob of viscose that obtains, further dehydrate.Therefore in above-mentioned steps (5), moisture blob of viscose is sent into whizzer and is dewatered, and the blob of viscose after the dehydration is sent into the moisture eliminator drying, namely gets rubber after the drying.Described whizzer is preferably horizontal centrifuge, and the preferred dynamically moisture eliminator of described moisture eliminator includes but not limited to fluidizing drying bed, spiral flash distillation dryer.
Generally, in above-mentioned steps (2) and step (4), send knockouts back to through the slurries after vibratory screening apparatus or the vibrating bed filtration, flocculation agent wherein can recycle.The washing water that can not utilize are delivered to treatment tank, treated qualified back discharging.
The polyisoprene rubber that the present invention makes adopts the general working method of rubber to carry out mixing and sulfuration.By 100 parts of newborn polyisoprene rubbers, 1.5 parts of stearic acid, 1 part of altax; 5 parts in zinc oxide; The proportioning that 40 parts of semi-reinforcing hydrocarbon blacks and sulphur are 1.5 parts two roller mills carry out mixing after, 145 ℃ of insulations are 50 minutes under certain pressure on the dull and stereotyped rubber vulcanizing machine, the gained rubber sample carries out performance test by national standard.The polyisoprene rubber that the present invention makes can be used for various tires, wire belt, travelling belt, sealing-ring, sebific duct, rubber overshoes and buffer block rubber item.
Embodiment:
Following examples are detailed description of the invention, can not be interpreted as it is restriction to technical solution of the present invention.
Example 1
At the bottom of polymeric kettle, lead to nitrogen after 15 minutes, add 110 parts of deionized waters to polymeric kettle, then with diethylamine tetraacethyls (EDTA) whole in the table 1, Sodium dodecylbenzene sulfonate (SBLS), sodium lauryl sulphate (SDS), dispersion agent (MF), tert-dodecyl mercaptan (DM), trisodium phosphate, NaHCO3, rongalite (SFS) stirring and dissolving is made into water, and isoprene monomer (IP) and benzoyl peroxide amine (BPO) stirring and dissolving are made into oil phase; 50 parts of deionized waters and ferrous sulfate (FeSO
4) stirring and dissolving is made into water.
10 ℃～30 ℃ of control temperature of reaction are carried out the dropping of fs, and the fs drips the combined amount of isoprene monomer (IP) and benzoyl peroxide amine (BPO) for its 5wt% that mixes total amount, drips ferrous sulfate (FeSO synchronously
4) amount be the 5wt% of its total amount, after the fs dropwises, the reaction 3h.After fs, reaction finished, carry out the dropping of subordinate phase again; Subordinate phase drips the combined amount of isoprene monomer (IP) and benzoyl peroxide amine (BPO) for its 15wt% that mixes total amount, drips ferrous sulfate (FeSO synchronously
4) amount be the 15wt% of its total amount, after subordinate phase dropwises, the reaction 3h.After the subordinate phase reaction finishes, carry out the dropping of phase III again; Phase III drips the remainder of isoprene monomer (IP) and benzoyl peroxide amine (BPO) combined amount, drips ferrous sulfate (FeSO synchronously
4) remainder, the phase III dropwises the back and continues reaction after 12～20 hours, obtains stable white polyisoprene aqueous emulsion.Polyreaction adds the termination agent diethanolamine of the 0.2wt% of isoprene weight, the antioxidant 264 of 1.0wt% after finishing, and transfers about pH8.0.Be warming up to 50 ℃, when steam charges into insulation, keep vacuum to remove residual monomer greater than 0.8Pa 1～5h.Its solid content is about 35.0%, pH8.0, particle diameter 80nm.
Example 2
At the bottom of polymeric kettle, lead to nitrogen after 15 minutes, add 110 parts of deionized waters to polymeric kettle, then with diethylamine tetraacethyls (EDTA) whole in the table 1, Sodium dodecylbenzene sulfonate (SBLS), sodium lauryl sulphate (SDS), dispersion agent (MF), tert-dodecyl mercaptan (DM), trisodium phosphate, NaHCO3, rongalite (SFS), stirring and dissolving is made into water, and isoprene monomer (IP) and benzoyl peroxide amine (BPO) stirring and dissolving are made into oil phase; 50 parts of deionized waters and ferrous sulfate (FeSO
4) stirring and dissolving is made into water.
10 ℃～30 ℃ of control temperature of reaction are carried out the dropping of fs, and the fs drips the combined amount of isoprene monomer (IP) and benzoyl peroxide amine (BPO) for its 8wt% that mixes total amount, drips ferrous sulfate (FeSO synchronously
4) amount be the 8wt% of its total amount, after the fs dropwises, the reaction 2h.After fs, reaction finished, carry out the dropping of subordinate phase again; Subordinate phase drips the combined amount of isoprene monomer (IP) and benzoyl peroxide amine (BPO) for its 12wt% that mixes total amount, drips ferrous sulfate (FeSO synchronously
4) amount be the 12wt% of its total amount, after subordinate phase dropwises, the reaction 2h.After the subordinate phase reaction finishes, carry out the dropping of phase III again; Phase III drips the combined amount remainder of isoprene monomer (IP) and benzoyl peroxide amine (BPO), drips ferrous sulfate (FeSO synchronously
4) remainder, dropwise the back and continue reaction after 12～20 hours, obtain stable white polyisoprene aqueous emulsion.Polyreaction adds the termination agent diethanolamine of the 0.2wt% of isoprene weight, the antioxidant 264 of 1.Owt% after finishing, and transfers about pH8.0.Be warming up to 50 ℃, charge into insulation simultaneously at steam, keep vacuum to remove residual monomer greater than 0.8Pa 1～5h.Its solid content is 36.5%, Ph7.8, particle diameter 120nm.
Example 3
At the bottom of polymeric kettle, lead to nitrogen after 15 minutes, add 110 parts of deionized waters to polymeric kettle, then with diethylamine tetraacethyls (EDTA) whole in the table 1, sodium lauryl sulphate (SDS), Sodium dodecylbenzene sulfonate, dispersion agent (MF), tert-dodecyl mercaptan (DM), trisodium phosphate, NaHCO3, rongalite (SFS), stirring and dissolving is made into water, and isoprene monomer (IP) and benzoyl peroxide amine (BPO) stirring and dissolving are made into oil phase; 50 parts of deionized waters and ferrous sulfate (FeSO
4) stirring and dissolving is made into water.
10 ℃～30 ℃ of control temperature of reaction are carried out the dropping of fs, and the fs drips the combined amount of isoprene monomer (IP) and benzoyl peroxide amine (BPO) for its 12wt% that mixes total amount, drips ferrous sulfate (FeSO synchronously
4) amount be the 12wt% of its total amount, after the fs dropwises, the reaction 1h.After fs, reaction finished, carry out the dropping of subordinate phase again; Subordinate phase is dripped the combined amount of the isoprene monomer that progressively increases (IP) and benzoyl peroxide amine (BPO) for its 18wt% that mixes total amount, drips ferrous sulfate (FeSO synchronously
4) amount be the 18wt% of its total amount, after subordinate phase dropwises, the reaction 1h.After the subordinate phase reaction finishes, carry out the dropping of phase III again; Phase III drips the remainder of the combined amount of isoprene monomer (IP) and benzoyl peroxide amine (BPO), drips ferrous sulfate (FeSO synchronously
4) remainder, dropwise the back and continue reaction after 12～20 hours, obtain stable white polyisoprene aqueous emulsion.After polyreaction finishes, add the antioxidant 264 of termination agent diethanolamine 1.0wt% of the 0.2wt% of isoprene weight, and transfer about pH8.0.Be warming up to 50 ℃, when steam charges into insulation, keep vacuum to remove residual monomer greater than 0.8Pa 1～5h.Its solid content is 38.5%, pH8.2, particle diameter 110nm.
Example 4
At the bottom of polymeric kettle, lead to nitrogen after 15 minutes, add 110 parts of deionized waters to polymeric kettle, then with diethylamine tetraacethyls (EDTA) whole in the table 1, Sodium dodecylbenzene sulfonate (SBLS), sodium lauryl sulphate (SDS), dispersion agent (MF), tert-dodecyl mercaptan (DM), trisodium phosphate, NaHCO3, rongalite (SFS), stirring and dissolving is made into water, and isoprene monomer (IP) and benzoyl peroxide amine (BPO) stirring and dissolving are made into oil phase; 50 parts of deionized waters, and ferrous sulfate (FeSO
4), stirring and dissolving is made into water.
10 ℃～30 ℃ of control temperature of reaction are carried out the dropping of fs, and the fs drips the combined amount of isoprene monomer (IP) and benzoyl peroxide amine (BPO) for its 15wt% that mixes total amount, drips ferrous sulfate (FeSO synchronously
4) amount be the 15wt% of its total amount, after the fs dropwises, the reaction 0.5h.After fs, reaction finished, carry out the dropping of subordinate phase again; Subordinate phase drips the combined amount of isoprene monomer (IP) and benzoyl peroxide amine (BPO) and mixes the 20wt% of total amount for it, drips synchronously and ferrous sulfate (FeSO
4) amount be the 20wt% of its total amount, after subordinate phase dropwises, the reaction 0.5h.After the subordinate phase reaction finishes, carry out the dropping of phase III again; Phase III drips the remainder of isoprene monomer (IP) and benzoyl peroxide amine (BPO), drips ferrous sulfate (FeSO synchronously
4) remainder, dropwise the back and continue reaction after 12～20 hours, obtain stable white polyisoprene aqueous emulsion.Polyreaction adds the termination agent diethanolamine of the 0.2wt% of isoprene weight, the antioxidant 264 of 1wt% after finishing, and transfers about pH8.0.Be warming up to 50 ℃, when steam charges into insulation, keep vacuum to remove residual monomer greater than 0.8Pa 1～5h.Its solid content is 38%, pH8.5, particle diameter 150nm.
Component in the polymerization of table 1 polyisoprene aqueous emulsion
Example 5
Get the polyisoprene aqueous emulsion of 100 parts of examples, 1 preparation, 0.5 part of sulphur and 0.5 part of zinc oxide of getting particle diameter 100-500 nanometer are mixed with water solution system, and ball milling obtained the aqueous dispersions of 500mg/h more than 72 hours then.Again the aqueous dispersions that obtains is joined in the polyisoprene aqueous emulsion and mix, carried out prevulcanized in 1 hour 40 ℃ of-60 ℃ of following insulated and stirred.Polyisoprene aqueous emulsion after the prevulcanized left standstill slaking after 24 hours under normal temperature laboratory, be the peptizer of 15～30% calcium nitrate aqueous solutions with the weight percent concentration for preparing, last gloves production line.
The dip forming process using ion deposition gelatinizing process of whole gloves, concrete steps are as follows:
1. mould cleans, and dries under 60～100 ℃ of conditions, and drying time is 0.5～5 minute;
2. soak peptizer, dry peptizer under 80～120 ℃ of conditions, drying time is 0.5～8 minute;
3. soak emulsion, under 60～100 ℃ of conditions, dry emulsion; Drying time is 0.5～5 minute;
4. leaching under 50～70 ℃ of conditions, crimping is handled;
5. crosslinked: carry out crosslinkedly under 80～120 ℃ of conditions, crosslinking time is 1～10 minute;
6. the demoulding;
7. wash with 50～80 ℃ of hot water, leaching obtains gloves and relevant slim emulsion products with aftertreatment.
Thickness 0.03～the 0.2mm of transparent latex glove, breaking tenacity is greater than 10MPa, and tension set is greater than 700%, and good hand touch, the rebound resilience of film are strong.
Example 6
Get the polyisoprene aqueous emulsion of 100 parts of examples, 2 preparations, 1 part of sulphur and 1 part of zinc oxide of getting particle diameter 100-500 nanometer are mixed with water solution system, and ball milling obtained the aqueous dispersions of 500mg/h more than 72 hours then.Again the aqueous dispersions that obtains is joined in the polyisoprene aqueous emulsion and mix, carried out prevulcanized in 1 hour 40 ℃ of-60 ℃ of following insulated and stirred.Polyisoprene aqueous emulsion after the prevulcanized left standstill slaking after 24 hours under normal temperature laboratory, be the peptizer of 15～30% calcium chloride waters with the weight percent concentration for preparing, last gloves production line.
The dip forming process using ion deposition gelatinizing process of whole gloves, concrete steps are as follows:
1. mould cleans, and dries under 60～100 ℃ of conditions, and drying time is 0.5～5 minute;
2. soak peptizer, dry peptizer under 80～120 ℃ of conditions, drying time is 0.5～8 minute;
3. soak emulsion, under 60～100 ℃ of conditions, dry emulsion; Drying time is 0.5～5 minute;
4. leaching under 50～70 ℃ of conditions, crimping is handled;
5. crosslinked: carry out crosslinkedly under 80～120 ℃ of conditions, crosslinking time is 1～10 minute;
6. the demoulding;
7. wash with 50～80 ℃ of hot water, leaching obtains gloves and relevant slim emulsion products with aftertreatment.
Thickness 0.03～the 0.2mm of transparent latex glove, breaking tenacity is greater than 10MPa, and tension set is greater than 700%, and good hand touch, the rebound resilience of film are strong.
Example 7
Get the polyisoprene aqueous emulsion of 100 parts of examples 3 preparation, get 2.0 parts of sulphur of particle diameter 100-500 nanometer, 1.0 parts of zinc oxide, 1 part of vulcanization accelerator BZ and be mixed with water solution system, ball milling obtained the aqueous dispersions of 500mg/h more than 72 hours then.Again the aqueous dispersions that obtains is joined in the polyisoprene aqueous emulsion and mix, carried out prevulcanized in 1.5 hours 40 ℃ of-60 ℃ of following insulated and stirred.Polyisoprene aqueous emulsion after the prevulcanized left standstill slaking after 24 hours under normal temperature laboratory, be the peptizer of 15～30% solder(ing)acids with the weight percent concentration for preparing, last gloves production line.
The dip forming process using ion deposition gelatinizing process of whole gloves, concrete steps are as follows:
1. mould cleans, and dries under 60～100 ℃ of conditions, and drying time is 0.5～5 minute;
2. soak peptizer, dry peptizer under 80～120 ℃ of conditions, drying time is 0.5～8 minute;
3. soak emulsion, under 60～100 ℃ of conditions, dry emulsion; Drying time is 0.5～5 minute;
4. leaching under 50～70 ℃ of conditions, crimping is handled;
5. crosslinked: carry out crosslinkedly under 80～120 ℃ of conditions, crosslinking time is 1～10 minute;
6. the demoulding;
7. wash with 50～80 ℃ of hot water, leaching obtains gloves and relevant slim emulsion products with aftertreatment.
Thickness 0.03～the 0.2mm of transparent latex glove, breaking tenacity is greater than 10MPa, and tension set is greater than 700%, and good hand touch, the rebound resilience of film are strong.
Example 8
Get the polyisoprene aqueous emulsion of 100 parts of examples 4 preparation, get 1.5 parts of sulphur of particle diameter 100-500 nanometer, 0.5 part of zinc oxide, 1 part of accelerant B Z and be mixed with water solution system, ball milling obtained the aqueous dispersions of 500mg/h more than 72 hours then.Again the aqueous dispersions that obtains is joined in the polyisoprene aqueous emulsion and mix, carried out prevulcanized in 1 hour 40 ℃ of-60 ℃ of following insulated and stirred.Polyisoprene aqueous emulsion after the prevulcanized left standstill slaking after 24 hours under normal temperature laboratory, be the peptizer of 15～30% zinc nitrate aqueous solutions with the weight percent concentration for preparing, last gloves production line.
The dip forming process using ion deposition gelatinizing process of whole gloves, concrete steps are as follows:
1. mould cleans, and dries under 60～100 ℃ of conditions, and drying time is 0.5～5 minute;
2. soak peptizer, dry peptizer under 80～120 ℃ of conditions, drying time is 0.5～8 minute;
3. soak emulsion, under 60～100 ℃ of conditions, dry emulsion; Drying time is 0.5～5 minute;
4. leaching under 50～70 ℃ of conditions, crimping is handled;
5. crosslinked: carry out crosslinkedly under 80～120 ℃ of conditions, crosslinking time is 1～10 minute;
6. the demoulding;
7. wash with 50～80 ℃ of hot water, leaching obtains gloves and relevant slim emulsion products with aftertreatment.
Thickness 0.03～the 0.2mm of transparent latex glove, breaking tenacity is greater than 10MPa, and tension set is greater than 700%, and good hand touch, the rebound resilience of film are strong.
Example 9
Get the polyisoprene aqueous emulsion of 100 parts of examples 4 preparation, get 1.5 parts of sulphur of particle diameter 100-500 nanometer, 0.5 part of zinc oxide, 1.5 parts of accelerant B Z and be mixed with water solution system, ball milling obtained the aqueous dispersions of 500mg/h more than 72 hours then.Again the aqueous dispersions that obtains is joined in the polyisoprene aqueous emulsion and mix, carried out prevulcanized in 2 hours 40 ℃ of-60 ℃ of following insulated and stirred.Polyisoprene aqueous emulsion after the prevulcanized left standstill slaking after 24 hours under normal temperature laboratory, be the peptizer of 15～30% zinc nitrate aqueous solutions with the weight percent concentration for preparing, last gloves production line.
The dip forming process using ion deposition gelatinizing process of whole gloves, concrete steps are as follows:
1. mould cleans, and dries under 60～100 ℃ of conditions, and drying time is 0.5～5 minute;
2. soak peptizer, dry peptizer under 80～120 ℃ of conditions, drying time is 0.5～8 minute;
3. soak emulsion, under 60～100 ℃ of conditions, dry emulsion; Drying time is 0.5～5 minute;
4. leaching under 50～70 ℃ of conditions, crimping is handled;
5. crosslinked: carry out crosslinkedly under 80～120 ℃ of conditions, crosslinking time is 1～10 minute;
6. the demoulding;
7. wash with 50～80 ℃ of hot water, leaching obtains gloves and relevant slim emulsion products with aftertreatment.
Thickness 0.03～the 0.2mm of transparent latex glove, breaking tenacity is greater than 10MPa, and tension set is greater than 650%, and good hand touch, the rebound resilience of film are strong.
Example 10
At the bottom of polymeric kettle, lead to nitrogen after 30 minutes, be made into water by 100 parts of deionized waters in the table 2, Sodium dodecylbenzene sulfonate SBLS, tert-dodecyl mercaptan (DM), Dispersant MF and NaHCO stirring and dissolving.IP, CHP all add the monomer still, and stirring and dissolving is made into oil phase.45 parts of deionized waters, whole FeSO
4Add the reductive agent still, stirring and dissolving is made into the aqueous solution.
15 ℃～30 ℃ of temperature of reaction of control are carried out the dropping of fs, and the progressively increase amount of isoprene monomer (IP) and hydrogen phosphide cumene (CHP) of fs is 10% of its total amount, drips ferrous sulfate (FeSO synchronously
4) amount be 10% of its total amount, after the fs dropwises, the reaction 1h.After fs, reaction finished, carry out the dropping of subordinate phase again; Subordinate phase progressively increase isoprene monomer (IP) and hydrogen phosphide cumene (CHP) amount for its total amount 20%, drip ferrous sulfate (FeSO synchronously
4) amount be 20% of its total amount, after subordinate phase dropwises, the reaction 2h.After the subordinate phase reaction finishes, carry out the dropping of phase III again; Progressively increase isoprene monomer (IP) and hydrogen phosphide cumene (CHP) remainder of phase III drips ferrous sulfate (FeSO synchronously
4) remainder, dropwise the back and continue reaction after 12～20 hours, obtain stable white polyisoprene aqueous emulsion.Polyreaction adds the termination agent diethanolamine of the 0.08wt% of polyisoprene water-based emulsion weight, the antioxidant 264 of 0.5wt% after finishing, and transfers about pH8.0.Be warming up to 50 ℃, remove residual monomer.Its solid content is 36%, pH7.8, particle diameter 110nm.
Drop into 80 parts of polyisoprene aqueous emulsions in knockouts, 20 parts of deionized waters stir.Drop into CaCl to the flocculation agent still
220 parts, 150 parts of deionized waters, stirring and dissolving.Add CaCl from the flocculation agent still to knockouts
2Solution adds in 40～60min.Adition process keeps knockouts to be in whipped state, and regulates the interior slurries pH of knockouts 5～7 with 0.5% sulphuric acid soln.Cohesion finished, and slurries are sent into rinse bath, with 2～3 times clear water agitator treatings 1～1.5 hour.Mixture after the washing filters through vibratory screening apparatus, obtains wet blob of viscose.Wet blob of viscose is sent into horizontal centrifuge dehydration 20～30min through conveying belt, send into spiral flash distillation dryer drying by feeding screw then, 110～130 ℃ of dryer inlet temperatures, material is the residence time 10～15s in moisture eliminator, can get the dried blob of viscose of water content＜1%.
The physical and mechanical properties of gained blob of viscose is as shown in table 3.
Example 11
Material consumption such as table 2, other processing condition are constant.The solid content that obtains emulsion is 36.2%, pH 7.1, particle diameter 183nm.The physical and mechanical properties of gained blob of viscose is as shown in table 3.
Example 12
At the bottom of polymeric kettle, lead to nitrogen after 30 minutes, be made into water by 100 parts of deionized waters in the table 2, nilox resin acid potash soap (DRS), tert-dodecyl mercaptan (DM), Dispersant MF and NaHCO stirring and dissolving.IP, CHP all add the monomer still, and stirring and dissolving is made into oil phase.45 parts of deionized waters, whole FeSO
4Add the reductive agent still, stirring and dissolving is made into the aqueous solution.
15 ℃～30 ℃ of temperature of reaction of control are carried out the dropping of fs, and the progressively increase amount of isoprene monomer (IP) and hydrogen phosphide cumene (CHP) of fs is 10% of its total amount, drips ferrous sulfate (FeSO synchronously
4) amount be 10% of its total amount, after the fs dropwises, the reaction 1h.After fs, reaction finished, carry out the dropping of subordinate phase again; Subordinate phase progressively increase isoprene monomer (IP) and hydrogen phosphide cumene (CHP) amount for its total amount 20%, drip ferrous sulfate (FeSO synchronously
4) amount be 20% of its total amount, after subordinate phase dropwises, the reaction 2h.After the subordinate phase reaction finishes, carry out the dropping of phase III again; Progressively increase isoprene monomer (IP) and hydrogen phosphide cumene (CHP) remainder of phase III drips ferrous sulfate (FeSO synchronously
4) remainder, dropwise the back and continue reaction after 12～20 hours, obtain stable white polyisoprene aqueous emulsion.Polyreaction adds the termination agent diethanolamine of the 0.3wt% of polyisoprene water-based emulsion weight, the antioxidant 264 of 2wt% after finishing, and transfers about pH8.0.Be warming up to 50 ℃, remove residual monomer.Its solid content is 37.5%, pH8.2, particle diameter 128nm.
Drop into 80 parts of polyisoprene aqueous emulsions in knockouts, 20 parts of deionized waters stir.Drop into CaCl to the flocculation agent still
220 parts, 150 parts of deionized waters, stirring and dissolving.Add CaCl from the flocculation agent still to knockouts
2Solution adds in 40～60min.Adition process keeps knockouts to be in whipped state, and regulates the interior slurries pH of knockouts 5～7 with 0.5% sulphuric acid soln.Cohesion finished, and slurries are sent into rinse bath, with 2～3 times clear water agitator treatings 1～1.5 hour.Mixture after the washing filters through vibratory screening apparatus, obtains wet blob of viscose.Wet blob of viscose is sent into horizontal centrifuge dehydration 20～30min through conveying belt, send into spiral flash distillation dryer drying by feeding screw then, 110～130 ℃ of dryer inlet temperatures, material is the residence time 10～15s in moisture eliminator, can get the dried blob of viscose of water content＜1%.
The physical and mechanical properties of gained blob of viscose is as shown in table 3.
Example 13
Material consumption such as table 2, other processing condition are constant.The solid content that obtains emulsion is 36.7%, pH 6.8, particle diameter 173.5nm.The physical and mechanical properties of gained blob of viscose is as shown in table 3.
Example 14
With CaCl in the flocculation agent still in the example 17
2Be adjusted into 17 parts, deionized water is 170 parts.CaCl
2The joining day of solution is extended for 70 minutes, and other processing condition are constant.The physical and mechanical properties of gained blob of viscose is as shown in table 3.
Example 15
With CaCl in the flocculation agent still in the example 19
2Be adjusted into 17 parts, deionized water is 170 parts.CaCl
2The joining day of solution is extended for 70 minutes, and other processing condition are constant.The physical and mechanical properties of gained blob of viscose is as shown in table 3.
Each component and consumption in the polymerization of table 2 methods of polyisoprene emulsion
Table 3 emulsion polyisoprene rubber physical and mechanical properties
Claims (67)
1. method with polyisoprene aqueous emulsion polymerization synthetic polyisoprene, be by the methods of polyisoprene emulsion after the degassing through cohesion, filter, washing, dry and get, it is characterized in that, specifically comprise following steps:
(1) add flocculation agent in methods of polyisoprene emulsion, stable methods of polyisoprene emulsion is the unstability cohesion under the flocculation agent effect, generates the slurries that contain the rubber blob of viscose;
(2) filter, blob of viscose is separated from slurries;
(3) washing: blob of viscose is changed in the washing bath, wash with water;
(4) filter: blob of viscose is separated from the slurries of washing;
(5) blob of viscose dewater, drying;
Described polyisoprene aqueous emulsion is to be monomer with the isoprene, is emulsification system with emulsifying agent, dispersion agent, adopts redox initiation system, under normal pressure and initiator initiation, obtains stable polyisoprene rubber emulsion through free-radical emulsion polymerization; It is characterized in that the mixed oil phase of described isoprene monomer and initiator adopts segmentation dropping mode to drip with the reductive agent in the redox initiation system together.
2. the method for claim 1 is characterized in that, described flocculation agent is selected a kind of in mineral acid, metal-salt, the polymeric flocculant for use.
3. method as claimed in claim 2 is characterized in that, described mineral acid is selected a kind of in hydrochloric acid, sulfuric acid, the nitric acid for use.
4. method as claimed in claim 2 is characterized in that, described metal-salt is a kind of in 1 valency, divalent, the 3 valency metal-salts.
5. method as claimed in claim 4 is characterized in that, described 1 valency metal-salt is Na
+Salt.
6. method as claimed in claim 5 is characterized in that, described Na
+Salt is NaCl.
7. method as claimed in claim 4 is characterized in that, described divalent metal-salt is Mg
2+, Ca
2+, Zn
2+Salt.
8. method as claimed in claim 7 is characterized in that, described Mg
2+Salt is MgCl
2, MgSO
4
9. method as claimed in claim 7 is characterized in that, described Ca
2+Salt is CaCl
2, Ca (NO
3)
2
10. method as claimed in claim 7 is characterized in that, described Zn
2+Salt is Zn (NO
3)
2
11. method as claimed in claim 4 is characterized in that, described 3 valency metal-salts are Al
3+Salt.
12. method as claimed in claim 11 is characterized in that, described Al
3+Salt is AlCl
3, Al
2(SO
4)
3
13. method as claimed in claim 2 is characterized in that, described polymeric flocculant is polyacrylamide.
14. method as claimed in claim 2 is characterized in that, described flocculation agent is CaCl
2With the combination of sulfuric acid, wherein CaCl
2As main flocculation agent, its consumption is 8～40wt% of emulsion total amount, and sulfuric acid is used for regulating the pH of slurries as coagulant aids.
15. method as claimed in claim 14 is characterized in that, described flocculation agent CaCl
2Being made into weight concentration with sulfuric acid is that 5～30% the aqueous solution uses.
16. method as claimed in claim 14 is characterized in that, described flocculation agent CaCl
2Being made into weight concentration with sulfuric acid is that 10～20% the aqueous solution uses.
17. method as claimed in claim 14 is characterized in that, described pH value control is 5～8.
18. method as claimed in claim 14 is characterized in that, described pH value control is 5.5～7.
19. the method for claim 1 is characterized in that, in above-mentioned steps (2), slurries and newborn polyisoprene rubber blob of viscose are sent into the rinse bath or the service sink that have whipping appts then by vibratory screening apparatus or vibrating bed filtering separation.
20. the method for claim 1 is characterized in that, in above-mentioned steps (3), blob of viscose is admitted to the rinse bath or the service sink that have whipping appts and washs, to remove a large amount of flocculation agent, emulsifying agent soluble impurity.
21. the method for claim 1 is characterized in that, in above-mentioned steps (4), the slurries of washing and blob of viscose are by vibratory screening apparatus or vibrating bed filtering separation.
22. the method for claim 1 is characterized in that, in above-mentioned steps (5), moisture blob of viscose is sent into whizzer and is dewatered, and the blob of viscose after the dehydration is sent into the moisture eliminator drying, namely gets rubber after the drying; Described whizzer is horizontal centrifuge, and described moisture eliminator is fluidizing drying bed or the spiral flash distillation dryer.
23. the method for claim 1 is characterized in that, in above-mentioned steps (2) and step (4), the slurries after filtering through vibratory screening apparatus or vibrating bed are sent knockouts back to, and flocculation agent wherein can recycle; The washing water that can not utilize are delivered to treatment tank, treated qualified back discharging
24. preparation method as claimed in claim 1 is characterized in that, described segmentation dropping mode is for being divided into three sections droppings; Wherein first section isoprene monomer and the mixed oil phase of initiator, reductive agent dripping quantity are respectively the 5wt-15wt% of total mass separately; Second section isoprene monomer and the mixed oil phase of initiator, reductive agent dripping quantity are respectively the 10wt-20wt% of total mass separately, and the 3rd section isoprene monomer and the mixed oil phase of initiator, reductive agent dripping quantity are respectively the 65wt-85wt% of total mass separately.
25. as claim 1 or 24 described preparation methods, it is characterized in that the purity of isoprene monomer reaches more than 98%.
26. preparation method as claimed in claim 1 is characterized in that, described initiator is selected superoxide for use, and consumption is 0.02～0.08wt% of isoprene monomer consumption.
27. preparation method as claimed in claim 26 is characterized in that, described superoxide adopts a kind of or both mixing in acyl peroxide class, the hydroperoxide kind.
28. preparation method as claimed in claim 27 is characterized in that, described acyl peroxide class is one or more the mixing in dibenzoyl peroxide amine, lauroyl peroxide amine, the decanoyl peroxide amine.
29. preparation method as claimed in claim 27 is characterized in that, described acyl peroxide class is dibenzoyl peroxide amine (BPO).
30. preparation method as claimed in claim 27, it is characterized in that described hydroperoxide kind is a kind of in hydrogen peroxide, pinane hydrogen peroxide, tertbutyl peroxide, hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide, hydrogen peroxide tri-isopropyl benzene, t-butyl hydroperoxide isopropyl benzene, the hydrogen peroxide chloro diisopropylbenzene(DIPB) or both and both above mixing.
31. preparation method as claimed in claim 27 is characterized in that, described hydroperoxide kind is tertbutyl peroxide or di-isopropylbenzene hydroperoxide.
32. preparation method as claimed in claim 27 is characterized in that, described hydroperoxide kind is tert-butyl peroxide.
33. preparation method as claimed in claim 1 is characterized in that, described emulsifying agent is a kind of in anionic emulsifier, the nonionic emulsifier or is two kinds blending emulsifiers.
34. preparation method as claimed in claim 33 is characterized in that, described anionic emulsifier is included as alkyl-sulphate, alkylsulfonate, alkylbenzene sulfonate, a kind of in the hard soap.
35. preparation method as claimed in claim 34 is characterized in that, described alkyl-sulphate is sodium lauryl sulphate.
36. preparation method as claimed in claim 34 is characterized in that, described alkylsulfonate is a kind of in sodium laurylsulfonate and the succsinic acid alkyl ester sodium sulfonate.
37. preparation method as claimed in claim 34 is characterized in that, described alkylbenzene sulfonate is Sodium dodecylbenzene sulfonate.
38. preparation method as claimed in claim 35 is characterized in that, described hard soap is sodium oleate, potassium oleate, a kind of in the nilox resin acid potash soap.
39. preparation method as claimed in claim 34 is characterized in that, described nonionic emulsifier is the alkylphenol polyoxyethylene.
40. preparation method as claimed in claim 34 is characterized in that, the consumption of described anionic emulsifier is 2～12wt% of isoprene monomer total amount.
41. preparation method as claimed in claim 34 is characterized in that, the consumption of described anionic emulsifier is the 4-10wt% of isoprene monomer total amount.
42. preparation method as claimed in claim 34 is characterized in that, the blending emulsifiers of described anionic emulsifier and nonionic emulsifying agent, and it makes up composite weight ratio is 9: 1-1: 9.
43. preparation method as claimed in claim 34 is characterized in that, the blending emulsifiers of described anionic emulsifier and nonionic emulsifying agent, and it makes up composite weight ratio and is preferably 5: 1～and 1: 5.
44., it is characterized in that the consumption of described blending emulsifiers is the 4-15wt% of isoprene monomer total amount as claim 42 or 43 described preparation methods.
45., it is characterized in that the consumption of described blending emulsifiers is the 4-10wt% of isoprene monomer total amount as claim 42 or 43 described preparation methods.
46. preparation method as claimed in claim 1, it is characterized in that, described dispersion agent is selected condensation formaldehyde naphthalene sulfonic acid salt for use, Dispersant MF, dispersion agent NF or the dispersion agent N that this condensation formaldehyde naphthalene sulfonic acid salt is commercial grade or the mixed dispersant of their two or more formations.
47. preparation method as claimed in claim 1 is characterized in that, described dispersant dosage is 0.05～1wt% of isoprene monomer total amount.
48. preparation method as claimed in claim 1 is characterized in that, described dispersant dosage is 0.1～0.8wt% of isoprene monomer total amount.
49. preparation method as claimed in claim 1 is characterized in that, the reductive agent consumption control in the redox initiation system is at the 0.22-2.6wt% of isoprene monomer total amount.
50. preparation method as claimed in claim 1 is characterized in that, the reductive agent consumption control in the redox initiation system is at the 0.22-1.3wt% of isoprene monomer total amount.
51. preparation method as claimed in claim 50, it is characterized in that described reductive agent is one or both and the two or more mixing in sodium bisulfite, sodium formaldehyde sulfoxylate, Sulfothiorine, V-Brite B, ferrous sulfate, iron protochloride, the xitix.
52. preparation method as claimed in claim 1 is characterized in that, selects the molecular weight of molecular weight regulator control polyisoprene for use.
53. preparation method as claimed in claim 52 is characterized in that, the consumption of described molecular weight regulator is the 0.05-0.8wt% of isoprene monomer total amount.
54. preparation method as claimed in claim 52 is characterized in that, the consumption of described molecular weight regulator is the 0.1-0.5wt% of isoprene monomer total amount.
55. preparation method as claimed in claim 52, it is characterized in that, described molecular weight regulator be just-DDM dodecyl mercaptan, just-14 carbon mercaptan, just-16 a kind of or two kinds and the two or more mixing in carbon mercaptan, uncle-DDM dodecyl mercaptan, uncle-14 carbon mercaptan, the uncle-16 carbon mercaptan.
56. preparation method as claimed in claim 52 is characterized in that, described molecular weight regulator for just-DDM dodecyl mercaptan or uncle-DDM dodecyl mercaptan.
57. preparation method as claimed in claim 1 is characterized in that, tank reactor is adopted in described polyisoprene aqueous emulsion polymerization, carries out under normal pressure; Temperature of reaction is 20～32 ℃, and total reaction time is between 25～40 hours, and reaction conversion ratio reaches 97.5% when above, adds terminator, anti-aging agent makes reaction terminating; Behind the reaction terminating, polyisoprene latex is sent into degassing still, remove unreacted monomer through flash distillation, gas.
58. preparation method as claimed in claim 1 is characterized in that, tank reactor is adopted in described polyisoprene aqueous emulsion polymerization, carries out under normal pressure; Temperature of reaction is 5～20 ℃, and total reaction time is between 30～60 hours; When reaction conversion ratio reaches 97.5% when above, add terminator, anti-aging agent makes reaction terminating; Behind the reaction terminating, polyisoprene latex is sent into degassing still, remove unreacted monomer through flash distillation, gas.
59. as claim 57 or 58 described preparation methods, it is characterized in that the terminator that described polyreaction adopts is a kind of in quinhydrones, Resorcinol, p-ten.-butylcatechol, MEHQ, diethanolamine, the Sodium dimethyldithiocarbamate 40min.
60., it is characterized in that the terminator that described polyreaction adopts is diethanolamine or Sodium dimethyldithiocarbamate 40min as claim 57 or 58 described preparation methods.
61., it is characterized in that the consumption of described terminator is the 0.05-0.5wt% of isoprene monomer total amount as claim 57 or 58 described preparation methods.
62., it is characterized in that the consumption of described terminator is the 0.1-0.3wt% of isoprene monomer total amount as claim 57 or 58 described preparation methods.
63., it is characterized in that the anti-aging agent that described polyreaction adopts is a kind of in phenols, amine, sulfurous esters, the thioesters class anti-aging agent as claim 57 or 58 described preparation methods.
64., it is characterized in that the anti-aging agent that described polyreaction adopts is phenolic type antioxidant as claim 57 or 58 described preparation methods.
65., it is characterized in that described phenolic type antioxidant is antioxidant 264, antioxidant 2246, anti-aging agent 246 as the described preparation method of claim 64, a kind of in antioxidant SP, the antioxidant d.
66., it is characterized in that the consumption of described anti-aging agent is the 0.2-4wt% of isoprene monomer total amount as claim 57 or 58 described preparation methods.
67., it is characterized in that the consumption of described anti-aging agent is the 0.3-2wt% of isoprene monomer total amount as claim 57 or 58 described preparation methods.
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| CN105348423A (en) * | 2015-10-25 | 2016-02-24 | 北京化工大学 | Low temperature-resistant polyisoprene elastomer and preparation method thereof |
| CN106032394A (en) * | 2015-03-17 | 2016-10-19 | 中国石油化工股份有限公司 | Polyisoprene rubber production method, and polyisoprene rubber and applications thereof |
| CN108264585A (en) * | 2018-02-01 | 2018-07-10 | 重庆金茂达特种橡胶有限公司 | Rubber production technology |
| CN108623858A (en) * | 2018-05-17 | 2018-10-09 | 合肥科天水性科技有限责任公司 | A kind of acid cure polymerizing preparation method of medical gloves |
| CN110860101A (en) * | 2019-12-11 | 2020-03-06 | 淄博鲁华泓锦新材料股份有限公司 | Method for removing organic solvent in polyisoprene latex |
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| CN101838360A (en) * | 2009-03-19 | 2010-09-22 | 上海生大医保股份有限公司 | Polyisoprene aqueous emulsion and method for preparing glove and related products |
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| CN101838360A (en) * | 2009-03-19 | 2010-09-22 | 上海生大医保股份有限公司 | Polyisoprene aqueous emulsion and method for preparing glove and related products |
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| CN106032394A (en) * | 2015-03-17 | 2016-10-19 | 中国石油化工股份有限公司 | Polyisoprene rubber production method, and polyisoprene rubber and applications thereof |
| CN106032394B (en) * | 2015-03-17 | 2017-08-22 | 中国石油化工股份有限公司 | The production method and isoprene rubber of a kind of isoprene rubber and its application |
| CN105348423A (en) * | 2015-10-25 | 2016-02-24 | 北京化工大学 | Low temperature-resistant polyisoprene elastomer and preparation method thereof |
| CN108264585A (en) * | 2018-02-01 | 2018-07-10 | 重庆金茂达特种橡胶有限公司 | Rubber production technology |
| CN108623858A (en) * | 2018-05-17 | 2018-10-09 | 合肥科天水性科技有限责任公司 | A kind of acid cure polymerizing preparation method of medical gloves |
| CN108623858B (en) * | 2018-05-17 | 2021-07-13 | 兰州科天健康科技股份有限公司 | Acid coagulation preparation method of medical gloves |
| CN110860101A (en) * | 2019-12-11 | 2020-03-06 | 淄博鲁华泓锦新材料股份有限公司 | Method for removing organic solvent in polyisoprene latex |
| CN110860101B (en) * | 2019-12-11 | 2024-02-13 | 淄博鲁华泓锦新材料集团股份有限公司 | Method for removing organic solvent in polyisoprene latex |
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