CN101220123A - Carboxylic acrylonitrile butadiene rubber latex, preparation and application thereof - Google Patents
Carboxylic acrylonitrile butadiene rubber latex, preparation and application thereof Download PDFInfo
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- CN101220123A CN101220123A CNA2007101992907A CN200710199290A CN101220123A CN 101220123 A CN101220123 A CN 101220123A CN A2007101992907 A CNA2007101992907 A CN A2007101992907A CN 200710199290 A CN200710199290 A CN 200710199290A CN 101220123 A CN101220123 A CN 101220123A
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- acrylonitrile butadiene
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Abstract
The invention provides a carboxy terminated nitrile latex with water resistance and high adhesive capacity, which uses butadiene, acrylonitrile, unsaturated carboxylic acid and vinyl acetate as monomers, uses a glyceryl laurate, inorganic salt, an evocating agent, a molecular weight regulator, etc. as raw materials of a auxiliary agent and is prepared by adding polymeric monomer for one time, adding the glyceryl laurate and molecular weight regulator for supplementation for the second time and emulsion polymerization technique of controlling temperature according to different sections. The physical property indexes of the carboxy terminated nitrile latex prepared by the invention are that: total solid is more than 45 percent; pH value is 7.5-8.5; viscosity is 30-100mPa s; surface tension is 35-50mN/m; intensity is 0.98 plus or minus 0.03g/cm<3>; particle diameter is 140-160nm; macrographic gel is less than or equal to 0.01 percent; binding nitrile is 33-36 percent. The latex is combined with poly vinyl acetate to obtain a carboxylate latex wood adhesive. Bonding strength reaches 1.5-2.0MPa. Bonded wood samples are cooked in boiled water for 3- 4 hours and the bonding position does not have glue failure; after the wood samples are dried, the bonding strength is not reduced.
Description
Technical field
The invention belongs to chemical field, relate to a kind of synthetic latex that is used for bonding wood materials, relate in particular to a kind ofly have a water resisting property, the carboxylic acrylonitrile butadiene rubber latex and the preparation thereof of high bonding force, the invention still further relates to the application of carboxylic acrylonitrile butadiene rubber latex---after carboxylic acrylonitrile butadiene rubber latex and aqueous polyvinyl acetate emulsion are composite, as wood adhesive.
Background technology
The kind of wood adhesive is a lot, but along with environmental protection requirement, Solvent Adhesive is eliminated gradually, and the tackiness agent of aq. type grows up gradually, wherein typical case's representative is aqueous polyvinyl acetate emulsion (popular name white glue with vinyl) and vinyl acetate and other monomeric multipolymer, as vinyl acetate and N hydroxymethyl acrylamide (96: 4) copolymer emulsion, vinyl acetate and single cyano ethyl maleic anhydride (96.5: 3.5) copolymer emulsion, also useful two kinds of wood adhesives that emulsion is shared, shared as acrylic latex and EVA latex, also there is report to use carboxylic styrene butadiene latex and isocyanic ester, the further complex reaction of Resins, epoxy generates the wood plywood tackiness agent of water resisting property.Therefore, develop water base asepsis environment-protecting, have a water resisting property, high strength latex is the development trend of wood adhesive.
Summary of the invention
The purpose of this invention is to provide a kind ofly have a water resisting property, the latex carboxylic acrylonitrile butadiene rubber latex of high bonding force.
Another object of the present invention provides a kind of preparation technology of latex carboxylic acrylonitrile butadiene rubber latex.
Carboxylic acrylonitrile butadiene rubber latex preparation method of the present invention comprises following processing step:
1. polymeric kettle is vacuumized, behind nitrogen replacement, press column weight amount proportioning and add 110～130 parts of de-salted waters successively, 3.2～4.4 parts of emulsifying agents, 0.5～2.5 part of tert-dodecyl mercaptan (molecular weight regulator), 0.3～0.5 part of sodium bicarbonate (pH value buffer reagent), 0.10～0.40 part in Repone K, 35～40 parts of vinyl cyanide, 3～6 parts of unsaturated carboxylic acids, 2～4 parts of vinyl acetates, 50～60 parts of divinyl, 0.30～0.55 part of Potassium Persulphate (initiator), 25 ± 2 ℃ of controlled temperature are reacted to 7～9 hours;
2. in polymeric kettle, add for the first time by 3～5 parts of de-salted waters, 0.10～0.2 part of emulsifying agent, 0.10～0.15 portion of mixed solution (with de-salted water dissolved emulsifier, molecular weight regulator) that molecular weight regulator is formed, be warming up to 40 ± 1 ℃, reacted 2～3 hours;
3. in polymeric kettle, add for the second time by 3～5 parts of de-salted waters, 0.10～0.2 part of emulsifying agent, 0.10～0.15 portion of mixed solution (with de-salted water dissolved emulsifier, molecular weight regulator) that molecular weight regulator is formed, be warming up to 55 ± 1 ℃, reacted 3～5 hours;
4. reach 99.0% when above when transformation efficiency, change above-mentioned system over to degassing still, the vacuum tightness of regulating degassing still to-0.070～-0.10MPa, add 0.003～0.01 part of Sodium Dimethyldithiocarbamate (terminator), adopt the vacuum extraction degassing after 1～1.5 hour then, transfer pH to 7.5～8.5 with alkali lye (5～10% potassium hydroxide solutions), filter promptly.
The emulsifying agent that the present invention adopts is the compound of sodium lauryl sulphate, Soxylat A 25-7 and Sodium dodecylbenzene sulfonate, and its weight proportion is 1: (1～0.5): 1; Unsaturated carboxylic acid in the monomer adopts methacrylic acid or vinylformic acid.
The physical performance index of the carboxylic acrylonitrile butadiene rubber latex of the present invention's preparation is as follows:
Total solid substance＞45%, pH value 7.5～8.5, viscosity 30～100mPas, surface tension 35～50mN/m, density 0.98 ± 0.03g/cm
3, particle diameter 140～160nm, macroscopical gel≤0.01% is in conjunction with nitrile 33～36%.
The latex carboxylic acrylonitrile butadiene rubber latex of the present invention preparation, with aqueous polyvinyl acetate emulsion composite the carboxylic acrylonitrile butadiene rubber latex wood adhesive: carboxylic acrylonitrile butadiene rubber latex and aqueous polyvinyl acetate emulsion mix promptly with 40%～60% and 60%～40% weight percent.Consistency was good after carboxylic acrylonitrile butadiene rubber latex mixed with aqueous polyvinyl acetate emulsion, precipitation precipitate≤0.5%; Bonding strength reaches 1.5～2.0Mpa, and bonding wood sample boiled in boiling water 3～4 hours, does not come unglued in the abutting edge, and after the wood sample oven dry, bonding strength does not subtract.
The present invention has following characteristics compared to existing technology:
1, the present invention adopts divinyl, vinyl cyanide, and unsaturated carboxylic acid, vinyl acetate and emulsifying agent carry out proportioning, especially use Vinyl Acetate Monomer and emulsifier polyoxyethylene ether, and this is to improve this latex and the composite key of aqueous polyvinyl acetate emulsion;
2, process using segmented mode of the present invention, promptly add emulsifying agent, molecular weight regulator by the some segmentation, the segmentation control reaction temperature, effectively prevented the generation of jello, reduced the speed in early stage of reaction, the different monomer of reactivity ratio relatively is evenly distributed on the macromolecular chain, improves the bonding force of latex.
3, technology of the present invention finishes back adding terminator and alkali lye in reaction, can make latex that tangible performance variation did not take place in storage period.
4, transformation efficiency height of the present invention reaches more than 99.0%.
5, the present invention adopts the degassing mode of vacuum extraction to remove the residual monomer of reaction system, makes latex reach environmental protection requirement.
Embodiment
Below by specific embodiment carboxylic acrylonitrile butadiene rubber latex of the present invention and preparation are elaborated.
Embodiment one:
The production technique of latex may further comprise the steps:
1, the process that feeds intake: at first polymeric kettle is vacuumized, use again nitrogen replacement, vacuum tightness reach-during 0.060Mpa, drop into 115 parts of de-salted waters successively, 1.0 parts of sodium alkyl sulfates, Soxylat A 25-7-10 are 0.8 part, 1.0 parts of Sodium dodecylbenzene sulfonatees, 0.3 part in Repone K, sodium bicarbonate; 0.30 part, 37 parts of vinyl cyanide, 1.0 parts of tert-dodecyl mercaptans, 4.0 parts of methacrylic acids, 3.0 parts of vinyl acetates stop to vacuumize; Add 56 parts of divinyl, add 0.40 part of 3% potassium persulfate solution at last as initiator (0.4 part of mass fraction that refers to Potassium Persulphate).
2, reaction is controlled and is added: 25 ± 2 ℃ of controlled temperature, continue to keep being reacted to 9 hours, and add and add liquid (wherein de-salted water is 5 parts, 0.05 part of sodium lauryl sulphate, 0.05 part of Sodium dodecylbenzene sulfonate, 0.15 part of tert-dodecyl mercaptan) for the first time.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, 0.05 part of Sodium dodecylbenzene sulfonate, 0.1 part of tert-dodecyl mercaptan) for the second time, put temperature in 40 minutes to 55 ± 1 ℃.Keep and be reacted to end.
3, remove residual monomer and aftertreatment: when transformation efficiency reaches more than 99%, in degassing still vacuum tightness be-during 0.10MPa, change latex the degassing of over to degassing still, add 0.003 part of Sodium Dimethyldithiocarbamate, 0.1 part of 10% potassium hydroxide solution, under the condition of insulation, vacuum extraction is removed residual monomer, and the degassing time is 1.5 hours.The last alkali lye (5% potassium hydroxide solution) that slowly adds is regulated pH value to 8, filters and packages.
The physical index of latex:
Total solid substance＞45%, pH value 7.5～8.5, viscosity≤100mPas, surface tension≤50mN/m, density 0.98 ± 0.03g/cm
3, particle diameter 140～160nm, macroscopical gel≤0.01% is in conjunction with nitrile 33～36%.
Application performance:
Carboxylic acrylonitrile butadiene rubber latex and aqueous polyvinyl acetate emulsion by 50%, 50% weight ratio mix wood adhesive.The two consistency postprecipitation precipitate≤0.2%.Bonding strength 1.75Mpa, bonding wood sample boiled in boiling water 3.5 hours, did not come unglued in the abutting edge, after the wood sample oven dry, and bonding strength 1.69Mpa.
Embodiment two, if monomeric proportioning is adjusted on the basis of example one: 40 parts of vinyl cyanide, 6.0 parts of methacrylic acids, 4.0 parts of vinyl acetates, 50 parts of divinyl, the consumption of other auxiliary agent is constant, and technology is identical, and then reaction gradient, the physical index produced are all in the scope of embodiment one.
Application performance: carboxylic acrylonitrile butadiene rubber latex: aqueous polyvinyl acetate emulsion 50: 50, consistency postprecipitation precipitate 0.2%.Bonding strength 1.97Mpa, bonding wood sample boiled in boiling water 3.5 hours, did not come unglued in the abutting edge, after the wood sample oven dry, and bonding strength 1.80Mpa.
Embodiment three, if monomeric proportioning is adjusted on the basis of example one: 35 parts of vinyl cyanide, 3.0 parts of methacrylic acids, 2.0 parts of vinyl acetates, 60 parts of divinyl, the consumption of auxiliary agent is constant, technological process is identical with example one, and the physical index of the latex of producing with this example is in the scope of embodiment one.
Application performance: carboxylic acrylonitrile butadiene rubber latex: aqueous polyvinyl acetate emulsion 50: 50, consistency postprecipitation precipitate 0.18%.Bonding strength 1.65Mpa, bonding wood sample boiled in boiling water 3.5 hours, did not come unglued in the abutting edge, after the wood sample oven dry, and bonding strength 1.60Mpa.
Embodiment four, if reducing de-salted water consumption total amount is 110 parts, originally add 102 parts, when adding for twice with each 4 parts of de-salted waters, 0.3 part of the consumption of initiator.The consumption of various emulsifying agents reduces by 3%, and the latex of being produced is identical with embodiment one.
Embodiment five, if emulsifying agent and the molecular weight regulator that cancellation is added for the second time, other component, technology are with example one.Polymerization reaction time ratio one will be grown 3 hours, macroscopical gel 0.2% of latex.During application, carboxylic acrylonitrile butadiene rubber latex: aqueous polyvinyl acetate emulsion 50: 50, consistency postprecipitation precipitate 1%.
Embodiment six, with the prepared carboxylic acrylonitrile butadiene rubber latex of embodiment one and aqueous polyvinyl acetate emulsion by 60%, 40% weight mix wood adhesive.Carboxylic acrylonitrile butadiene rubber latex and aqueous polyvinyl acetate emulsion consistency postprecipitation precipitate 0.18%.Bonding strength 1.95Mpa, bonding wood sample boiled in boiling water 4.0 hours, did not come unglued in the abutting edge, after the wood sample oven dry, and bonding strength 1.89Mpa.
Embodiment seven, with the prepared carboxylic acrylonitrile butadiene rubber latex of embodiment one and aqueous polyvinyl acetate emulsion by 40%, 60% weight mix wood adhesive.Carboxylic acrylonitrile butadiene rubber latex and aqueous polyvinyl acetate emulsion consistency postprecipitation precipitate 0.10%.Bonding strength 1.68Mpa,, bonding wood sample boiled in boiling water 3.0 hours, and do not come unglued in the abutting edge, after the wood sample oven dry, bonding strength 1.62Mpa.
Claims (5)
1. the preparation method of a carboxylic acrylonitrile butadiene rubber latex comprises following processing step:
1. polymeric kettle is vacuumized, behind nitrogen replacement, press column weight amount proportioning and add 110～130 parts of de-salted waters successively, 3.2～4.4 parts of emulsifying agents, 0.5～2.5 part of tert-dodecyl mercaptan, 0.3～0.5 part of sodium bicarbonate, 0.10～0.40 part in Repone K, 35～40 parts of vinyl cyanide, 3～6 parts of unsaturated carboxylic acids, 2～4 parts of vinyl acetates, 50～60 parts of divinyl, 0.30～0.55 part of Potassium Persulphate, 25 ± 2 ℃ of controlled temperature are reacted to 7～9 hours;
2. for the first time in polymeric kettle, add 3～5 parts of de-salted waters, 0.10～0.2 part of emulsifying agent, 0.10～0.15 part of molecular weight regulator is warming up to 40 ± 1 ℃, reacts 2～3 hours;
3. for the second time add 3～5 parts of de-salted waters, 0.15～0.20 part of emulsifying agent, 0.10～0.15 part of molecular weight regulator is warming up to 55 ± 1 ℃, reacts 3～5 hours;
4. reach 99.0% when above when transformation efficiency, change above-mentioned system over to degassing still, the vacuum tightness of regulating degassing still to-0.070～-0.10MPa, add 0.003～0.01 part of terminator Sodium Dimethyldithiocarbamate, adopt the vacuum extraction degassing after 1～1.5 hour then,, filter promptly with lye pH adjustment to 7.5～8.5.
2. the preparation method of carboxylic acrylonitrile butadiene rubber latex according to claim 1, it is characterized in that: described emulsifying agent is the compound of sodium lauryl sulphate, Soxylat A 25-7 and Sodium dodecylbenzene sulfonate, its weight proportion is 1: (1～0.5): 1.
3. the preparation method of carboxylic acrylonitrile butadiene rubber latex according to claim 1, it is characterized in that: described unsaturated carboxylic acid is methacrylic acid or vinylformic acid.
4. the carboxylic acrylonitrile butadiene rubber latex of method preparation according to claim 1, its physical performance index is as follows: total solid substance＞45%, pH value 7.5～8.5, viscosity 30～100mPa.s, surface tension 35～50 mN/m, density 0.98 ± 0.03g/cm
3, particle diameter 140～160nm, macroscopical gel≤0.01% is in conjunction with nitrile 33～36%.
5. the carboxylic acrylonitrile butadiene rubber latex of method preparation according to claim 1 is used to prepare wood adhesive: carboxylic acrylonitrile butadiene rubber latex and aqueous polyvinyl acetate emulsion are mixed promptly with 40%～60% and 60%～40% weight percent.
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| CNA2007101992907A CN101220123A (en) | 2007-12-01 | 2007-12-01 | Carboxylic acrylonitrile butadiene rubber latex, preparation and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483499A (en) * | 2013-09-27 | 2014-01-01 | 安庆华兰科技有限公司 | Preparation method for carboxylic acrylonitrile butadiene rubber latex for industrial and medical impregnated checking gloves |
| 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 |
| CN105237682A (en) * | 2015-10-19 | 2016-01-13 | 杭州蓝诚实业有限公司 | Method for preparing high performance carboxylic acrylonitrile butadiene rubber latexes |
| CN105837754A (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 |
| CN107236083A (en) * | 2017-06-07 | 2017-10-10 | 东营九洲奥华化工有限责任公司 | Modified graphene nitrile rubber latex and its production technology |
| JP2018028048A (en) * | 2016-08-19 | 2018-02-22 | 旭化成株式会社 | Copolymer Latex |
| CN112940184A (en) * | 2021-03-08 | 2021-06-11 | 湖北分聚新材料有限公司 | Preparation method of butyronitrile latex for high-strength gloves |
| CN113457600A (en) * | 2021-07-28 | 2021-10-01 | 山东广浦生物科技有限公司 | Preparation device and preparation process of high-performance carboxylic butyronitrile latex |
| CN113501915A (en) * | 2021-09-13 | 2021-10-15 | 亚蓝湾(山东)新材料科技有限责任公司 | Modified carboxylic acrylonitrile butadiene latex and preparation method thereof |
| CN113563515A (en) * | 2021-06-30 | 2021-10-29 | 江西岳峰集团环保新材有限公司 | Preparation method of high-performance carboxylic acrylonitrile butadiene latex |
-
2007
- 2007-12-01 CN CNA2007101992907A patent/CN101220123A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103483499A (en) * | 2013-09-27 | 2014-01-01 | 安庆华兰科技有限公司 | Preparation method for carboxylic acrylonitrile butadiene rubber latex for industrial and medical impregnated checking gloves |
| CN105837754B (en) * | 2015-01-15 | 2018-09-04 | 中国石油天然气股份有限公司 | Preparation method of carboxyl nitrile rubber |
| CN105837754A (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 |
| CN105237682A (en) * | 2015-10-19 | 2016-01-13 | 杭州蓝诚实业有限公司 | Method for preparing high performance carboxylic acrylonitrile butadiene rubber latexes |
| JP2018028048A (en) * | 2016-08-19 | 2018-02-22 | 旭化成株式会社 | Copolymer Latex |
| CN107236083A (en) * | 2017-06-07 | 2017-10-10 | 东营九洲奥华化工有限责任公司 | Modified graphene nitrile rubber latex and its production technology |
| CN112940184A (en) * | 2021-03-08 | 2021-06-11 | 湖北分聚新材料有限公司 | Preparation method of butyronitrile latex for high-strength gloves |
| CN113563515A (en) * | 2021-06-30 | 2021-10-29 | 江西岳峰集团环保新材有限公司 | Preparation method of high-performance carboxylic acrylonitrile butadiene latex |
| CN113563515B (en) * | 2021-06-30 | 2024-04-09 | 江西岳峰集团环保新材有限公司 | Preparation method of high-performance carboxylated nitrile latex |
| CN113457600A (en) * | 2021-07-28 | 2021-10-01 | 山东广浦生物科技有限公司 | Preparation device and preparation process of high-performance carboxylic butyronitrile latex |
| CN113501915A (en) * | 2021-09-13 | 2021-10-15 | 亚蓝湾(山东)新材料科技有限责任公司 | Modified carboxylic acrylonitrile butadiene latex and preparation method thereof |
| CN113501915B (en) * | 2021-09-13 | 2021-11-30 | 亚蓝湾(山东)新材料科技有限责任公司 | Modified carboxylic acrylonitrile butadiene latex and preparation method thereof |
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