CN1367186A - Preparation method of carboxy-nitril latex with high strong action for impregnating product - Google Patents
Preparation method of carboxy-nitril latex with high strong action for impregnating product Download PDFInfo
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- CN1367186A CN1367186A CN 01123472 CN01123472A CN1367186A CN 1367186 A CN1367186 A CN 1367186A CN 01123472 CN01123472 CN 01123472 CN 01123472 A CN01123472 A CN 01123472A CN 1367186 A CN1367186 A CN 1367186A
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Abstract
A preparation method of carboxy nitrile latex for making lining-free oil-proofing industrial glove includes the folloiwng steps: adding desalted water 80-150 portions, emulsifier 2.5-4.0 portions, molecular weight regulator 0.7-1.5 portions, pH buffering agent 0.1-0.6 portions, polymerization monomer butadiene 50-65 portions, acrylonitrile 35-45 portions, unsaturated carboxylic acid C 3-10 portions, unsaturated carboxylic ester C 1-8 portions/vinyl carboxylic ester D 1-4 portions, and finally adding initiating agent 0.1-1.0 portions, first stage the temp. is 20-30 deg.C; adding acrylointrile 0-10 portions, unsaturated acid C 1-2 portions, unsaturated carboxylic ester C 0.5-1 portions, vinyl carboxylic ester 0.5-1 portions and residue monomer to make continuous reaction, adding first emulsifier, reducing agent additive liquor, making reaction for 12 hr., adding second and third additive liquors, making reaction until the conversion rate is up to above 97% so as to obtain the invented product. It can improve the flexibility of latex products.
Description
The invention belongs to make linerless in the synthetic latex technology of oil resistant industrial gloves, be the preparation method of a kind of dipped goods of extra-high-speed brute force with carboxylic acrylonitrile butadiene rubber latex
Industrial gloves is the appliances for labor protection of field of petrochemical industry in linerless, is divided into light expert cover, suede expert cover, and this gloves require oil resistant, tear fracture brute force 〉=25MPa.Its used raw material mainly is the principal element of modified carboxyl nitrile rubber.This modified carboxyl butadiene-acrylonitrile rubber lactonitrile content is higher, in conjunction with nitrile between 35-38%.The latex product of high-nitrile, oil-proofness is good, and tear fracture is powerful high.But the weak point of high-nitrile is goods hardens, and the wearing comfort is poor.In order to improve the deficiency of this respect, just to use the 4th, the 5th monomer modifiedly, the 4th, the 5th monomer is used esters of unsaturated carboxylic acids more.As methyl methacrylate, the polysubstituted thing of hydroxyl esters of unsaturated carboxylic acids or unsaturated carboxylic acid ester group etc. can improve the flexibility of superpolymer, the brute force that can not lose superpolymer again.Four, the 5th monomeric consumption and all monomer adding modes are the keys of modification.Especially the actual of nitrile is the gordian technique that this latex is produced in conjunction with situation.Nitrile rubber, especially high nitrile rubber breast, the exothermic heat of reaction fierceness, the mechanical stability of latex is relatively poor, selects suitable emulsification system extremely important.Emulsification system should keep pH value vary stable and certain mechanical stability in reaction process, have the characteristics to the susceptibility (unstable) of dipping calcium ion again.Emulsification system adopts the polynary compound system of nonionic emulsifying agent and anionic emulsifier more.Initiator system mainly adopts the elevated temperature heat initiator system and the oxidation-reduction low temperature polymerization of persulphate.How the method that removes residual monomer also has method with chemical method and usefulness with decompression gas formulation.Degassing equipment is the support condition of this technology.Rerum natura for the product that guarantees latex adds auxiliary agents such as anti-aging agent in latex, add the stability of alkali with pH value in the maintenance system.For this reason, the U.S., Germany, Japanese firm innovate at monomer system, emulsification system, initiator system, processing condition, the aspects such as method of deviating from residual monomer, have independently formed unique technique.
The object of the invention is to provide a kind of latex product flexibility of improving, prevent that gel from producing, reduce the speed in early stage of reaction, improve the physical and chemical performance of latex product, make latex the dipped goods of extra-high-speed brute force of tangible performance variation not take place with the preparation method of carboxylic acrylonitrile butadiene rubber latex in storage period.
The present invention adopts following technical scheme:
1) monomer divides three addings, adds the semi-continuous emulsion polymerizing method of emulsifying agent and reductive agent three times.Initiator system is the oxidation-reduction system.Temperature is controlled to be the ladder temperature control.Temperature range 20-65 ℃.
2) synthetic set of dispense ratio: divinyl 40-60 part, vinyl cyanide 35-45 part, unsaturated carboxylic acid C3-8 part, esters of unsaturated carboxylic acids C 0-8 part, vinyl carboxyl ester D 0--3-4 part, emulsifying agent is sodium lauryl sulphate, OP, Sodium dodecylbenzene sulfonate, diffusant.The emulsifying agent consumption is 1.2-5.4 part, initiator 0.09-0.55 part, and molecular weight regulator 0.1-3.5 part, pH value buffer reagent is 0.3-0.5 part, and inorganic salt are 0.05-0.40 part, and de-salted water is 80-150 part, and terminator is 45-390ppm.
3) technological process:
Under vacuum, drop into soft water, partial emulsifier, molecular weight regulator, pH buffer reagent, partial monosomy in proportion, add initiator and partial reduction agent at last.By three sections temperature of reaction requirement temperature controls, by adding some an adding emulsifying agent and a reductive agent, partial monosomy.Transformation efficiency reaches more than 45.0%, the processing that outgases, and pH reaches between the 7-8 with alkali lye impregnation breast, adds terminator at last.
The present invention improves the latex product flexibility.Prevent that gel from producing, reduce the speed in early stage of reaction, the different monomer of reactivity ratio relatively is evenly distributed on the polymer key, improve the physical and chemical performance of latex product, improve processing performance.Make latex that tangible performance variation not take place in storage period.The latex that uses the present invention to produce, during auxiliary agents such as interpolation vulcanizing agent, precipitation precipitate≤0.5%.Film forming speed is fast, but 10s film forming 0.45-0.55mm.Glued membrane is easy to take off from fingerprint, yield rate 〉=95%.Before aging, elongation 〉=580%, tensile strength at yield 30MPa.After aging, elongation 〉=500%, tensile strength at yield 〉=25MPa.
Accompanying drawing of the present invention is a process flow diagram.
The embodiment of the invention is as follows:
Example one:
1. latex production
1) process that feeds intake: at first polymeric kettle is vacuumized, use nitrogen replacement again, vacuum tightness reaches-during 0.10Mpa, drop into 115 parts of de-salted waters successively, 1.0 parts of sodium alkyl sulfates, the ninth of the ten Heavenly Stems, phenolic group Soxylat A 25-7-10 was 0.8 part, 0.8 part of Sodium dodecylbenzene sulfonate, diffusion agent N F0.2 part, 0.3 part in inorganic salt, 0.30 part of pH buffer agent solution, 30 parts of vinyl cyanide, 1.0 parts of molecular weight regulators, 4.0 parts of unsaturated carboxylic acid C (vinyl carboxyl), esters of unsaturated carboxylic acids C3.0 part, esters of unsaturated carboxylic acids D1.0 part stops to vacuumize.Add 50 parts of divinyl, add 0.40 part of initiator solution at last.
2) reaction is controlled and is added: 25 ± 2 ℃ of controlled temperature, keep reaction 6 hours, and add residual monomer (10 parts of vinyl cyanide, unsaturated carboxylic acid C1.0 part, esters of unsaturated carboxylic acids C0.5 part, esters of unsaturated carboxylic acids D0.5 part), continue to keep being reacted to 9 hours, adding is added liquid for the first time, and (wherein de-salted water is 5 parts, 0.05 part of sodium lauryl sulphate, OP0.04 part, 0.04 part of Sodium dodecylbenzene sulfonate, 0.001 part of diffusant, 0.15 part of reductive agent).Put temperature in 40 minutes to 40 ± 1 ℃.Keep reaction 3 hours.Add and add liquid (wherein de-salted water is 5 parts, 0.05 part of sodium lauryl sulphate, OP0.04 part, 0.04 part of Sodium dodecylbenzene sulfonate, diffusion agent N F0.001 part, 0.1 part of reductive agent) for the second time, put temperature in 40 minutes to 55 ± 1 ℃.Keep and be reacted to end.
3) remove residual monomer and aftertreatment: transformation efficiency reaches 45% when above, and stopped reaction in degassing still vacuum tightness be-during 0.10MPa, change latex over to degassing still and outgas, and removes residual monomer, and the degassing time is 1.5 hours.The back slowly adds alkali lye and regulates the pH value to 7-8, adds terminator 200ppm again, filters and packages at last.
2. the physical index of latex
(1) total solid substance " 45%, (2) pH value 7-8 (3) viscosity≤100mPas (4) surface tension≤50mN/m (5) density 0.98 ± 0.03g/cm
3(6) particle diameter 140-160nm (7) structural gel≤35% (8) macroscopical gel≤0.01% (9) is in conjunction with nitrile 34-36%, (10) combined acid 35-45%.
3. application performance 1) Technological adaptability is good, and curing temperature 110-120 ℃.Good stability when 2) adding vulcanization aid, precipitation precipitate≤0.5%.3) glued membrane is bright and clean bright in vain.4) film forming speed is fast, but 10s film forming 0.45-0.55mm.Glued membrane is easy to take off from fingerprint, yield rate 〉=95%.5) mechanical property of aging front and back: before aging, elongation 〉=580%, tensile strength at yield 35MPa.After aging, elongation 〉=500%, tensile strength at yield 〉=35MPa.
Example two: if esters of unsaturated carboxylic acids C does not use, only use esters of unsaturated carboxylic acids D, total consumption is 3.0 parts, originally add 2.0 parts, add 1.0 parts in batches, 52 parts of divinyl, the consumption of other monomer and auxiliary agent is constant, technology is identical, and then reaction gradient, the physical index of being produced, application indexes are all in example one scope.
Example three: if without esters of unsaturated carboxylic acids D, the total amount of esters of unsaturated carboxylic acids C is 5.0 parts, originally adds 4.0 parts, divide and add 1.0 parts, the consumption of other monomer and auxiliary agent is constant, and technological process is identical with example one, and the physical index of the latex of producing with this example and application indexes are still in the scope of example one.
Example four: if do not take the mode that adds in batches, monomeric kind, proportioning and example one or example two, example three are identical, and the consumption of initiator should be 0.30 part, and originally temperature of reaction is controlled at 25 ± 1 ℃.Other auxiliary dosage and technology are identical with example one, and the latex of being produced is identical with example one.
Example five: if reduce de-salted water consumption total amount is 110 parts, originally adds 102 parts, when adding for twice with each 4 parts of de-salted waters, and 0.3 part of the consumption of initiator.The consumption of various emulsifying agents reduces by 3%, and the latex of producing by this example is identical with example one.
Example six: if reduce the consumption to 37 part (originally add 30 parts, divide and add 7 parts) of vinyl cyanide, the divinyl consumption increases to 53 parts, and the consumption of initiator is reduced to 0.30 part, and other monomer and auxiliary dosage, technology are identical with example one.The physical index of the latex of producing by this example and application indexes are still in example one scope.
Example seven: if the vinyl cyanide consumption is 37 parts, 53 parts of divinyl, initiator are 0.25 part, and other monomer, auxiliary dosage, processing condition are identical with example four, and the physical index of the latex of being produced and application indexes are still in the scope of example one.
Example eight: if emulsifying agent and reductive agent that cancellation is added for the second time, other component, technology are with example one.
Physical Property Analysis index: particle diameter 160-180nm, surface tension≤40mN/m, structural gel＞60%, viscosity＞100mPas.
Application result: the film-forming properties of latex is poor, can not satisfy the requirement of process industry gloves.
Claims (3)
1. the dipped goods of an extra-high-speed brute force is with the preparation method of carboxylic acrylonitrile butadiene rubber latex, it is characterized in that: the intermittent type emulsion polymerization technique of the disposable adding of polymerization single polymerization monomer, four addings emulsifying agent, reductive agent and molecular weight regulators, initiator system is the oxidation-reduction system; Specific embodiment is as follows: polymeric kettle vacuumizes, use nitrogen replacement, add de-salted water 80-150 part then by weight ratio successively, emulsifying agent 2.5-4.0 part, molecular weight regulator 0.7-1.5 part, pH buffer reagent 0.1-0.6 part, add polymerization single polymerization monomer divinyl 50-65 part again, vinyl cyanide 35-45 part, unsaturated carboxylic acid C3-10 part, esters of unsaturated carboxylic acids C1-8 part/vinyl carboxylate D1-4 part, add initiator 0.1-1.0 part at last, three periods ladder temperature control fs are 20-30 ℃, keep reaction 6 hours, add vinyl cyanide 0-10 part, unsaturated acid C1-2 part, esters of unsaturated carboxylic acids C0.5-1 part, vinyl carboxylate 0.5-1 part residual monomer continues to keep and is reacted to 9 hours, add and add liquid (emulsifying agent for the first time, reductive agent accounts for the 3-7% of its gross weight), be warmed up to 30-40 ℃, keep being reacted to 12 hours, add emulsifying agent, the 3-6% that reductive agent accounts for its gross weight adds liquid for the second time, be warmed up to 40-55 ℃, keep being reacted to 14 hours, add emulsifying agent, the 3-6% that reductive agent accounts for its gross weight adds liquid for the third time, keeps to be reacted to transformation efficiency and to reach 97% when above, stopped reaction removes residual monomer and aftertreatment then.
2. the dipped goods of a kind of extra-high-speed brute force according to claim 1 preparation method of carboxylic acrylonitrile butadiene rubber latex, it is characterized in that: initiator system is the oxidation-reduction system; Temperature is controlled to be three sections ladder temperature controls, 20 ℃-55 ℃ of temperature ranges,
3. the dipped goods of a kind of extra-high-speed brute force according to claim 1 preparation method of carboxylic acrylonitrile butadiene rubber latex, it is characterized in that: obtaining the carboxylic acrylonitrile butadiene rubber latex performance is: total solid substance 〉=45%, pH7-8, viscosity≤100mPa.S, surface tension≤50mN/m, density=0.98-1.01g/cm
3, particle diameter 130-160nm, structural gel≤30%, macroscopical gel≤0.01%, its product properties: powerful greater than 30Mpa, elongation is greater than 400%.
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| CN 01123472 CN1200021C (en) | 2001-07-26 | 2001-07-26 | Preparation method of carboxy-nitril latex with high strong action for impregnating product |
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| CN 01123472 CN1200021C (en) | 2001-07-26 | 2001-07-26 | Preparation method of carboxy-nitril latex with high strong action for impregnating product |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103228688A (en) * | 2010-09-30 | 2013-07-31 | 高产有限公司 | Elastomer rubber and elastomer product that do not use vulcanization accelerator or sulfur |
| CN103788298A (en) * | 2012-10-30 | 2014-05-14 | 福盈科技化学股份有限公司 | Preparation method of carboxylated nitrile latex and article prepared from carboxylated nitrile latex |
| CN105418846A (en) * | 2015-12-21 | 2016-03-23 | 安庆华兰科技有限公司 | Preparation method for high strength and high abrasion resistance carboxylated nitrile butadiene rubber latex for nitrile gloves |
| CN105837753A (en) * | 2015-01-15 | 2016-08-10 | 中国石油天然气股份有限公司 | Preparation method of carboxyl nitrile rubber |
-
2001
- 2001-07-26 CN CN 01123472 patent/CN1200021C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103228688A (en) * | 2010-09-30 | 2013-07-31 | 高产有限公司 | Elastomer rubber and elastomer product that do not use vulcanization accelerator or sulfur |
| CN103228688B (en) * | 2010-09-30 | 2015-05-06 | 高产有限公司 | Elastomer rubber and elastomer product that do not use vulcanization accelerator or sulfur |
| CN103788298A (en) * | 2012-10-30 | 2014-05-14 | 福盈科技化学股份有限公司 | Preparation method of carboxylated nitrile latex and article prepared from carboxylated nitrile latex |
| CN105837753A (en) * | 2015-01-15 | 2016-08-10 | 中国石油天然气股份有限公司 | Preparation method of carboxyl nitrile rubber |
| CN105837753B (en) * | 2015-01-15 | 2018-10-16 | 中国石油天然气股份有限公司 | Preparation method of carboxyl nitrile rubber |
| CN105418846A (en) * | 2015-12-21 | 2016-03-23 | 安庆华兰科技有限公司 | Preparation method for high strength and high abrasion resistance carboxylated nitrile butadiene rubber latex for nitrile gloves |
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