CN1058726C - Carboxyl acrylonitrile-butadiene rubber powder and its prepn. tech. - Google Patents
Carboxyl acrylonitrile-butadiene rubber powder and its prepn. tech. Download PDFInfo
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- CN1058726C CN1058726C CN97107122A CN97107122A CN1058726C CN 1058726 C CN1058726 C CN 1058726C CN 97107122 A CN97107122 A CN 97107122A CN 97107122 A CN97107122 A CN 97107122A CN 1058726 C CN1058726 C CN 1058726C
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- acrylonitrile
- carboxyl
- butadiene rubber
- rubber powder
- butadiene
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Abstract
The present invention relates to carboxylic acrylonitrile butadiene rubber powder and a preparation process thereof, wherein the components of carboxylic acrylonitrile butadiene rubber comprise butadiene, acrylonitrile and unsaturated hydrocarbon containing carboxyl, the weight percentage of the butadiene, the acrylonitrile and the unsaturated hydrocarbon is from 55 to 93%, from 4 to 43% and from 1 to 6% respectively. The present invention is characterized in that in emulsion polymerization, a compound emulsifier containing an amphoteric emulsifier, a peroxide initiator and dodeca mercaptan are added in sequence, and the binary copolymerization of acrylonitrile and butadiene is carried out to prepare butadiene-acrylonitrile latex at the reaction temperature of 45 to 75DEGC; the pH value of emulsion is controlled to 6.5 to 7, the unsaturated hydrocarbon containing carboxyl and peroxide are added at the reaction temperature of 65 to 70DEGC, and micro powdery suspension is obtained after 1 to 3 hours of reaction.
Description
The invention belongs to homopolymer or multipolymer, have at least a unsaturated aliphatic base to have two or more carbon-to-carbon double bond classes with one or more unsaturated aliphatic base things.
Present carboxy nitrile rubber adopts divinyl, vinyl cyanide adds vinylformic acid and the derivative terpolymer forms, carboxyl is on main polymer chain, polymkeric substance is linear, the non-crosslinked type, profile is block or aqueous, micelle after the polymerization is that 0.1-0.3um is spherical, can not printing opacity, generally be used for rubber item wear-resisting, high strength oil resistant occasion.
The objective of the invention is to avoid above-mentioned weak point of the prior art and provide a kind of employing to contain carboxyl unsaturated hydrocarbons grafting paracril make carboxyl acrylonitrile-butadiene rubber powder, greatly improve the consistency of itself and polyvinyl chloride resins such as (PVC), improve the shock resistance of resins such as PVC.
Purpose of the present invention can reach by following measure:
A kind of carboxyl acrylonitrile-butadiene rubber powder and preparation technology thereof, wherein the carboxy nitrile rubber component is divinyl, vinyl cyanide, contains the carboxyl unsaturated hydrocarbons, its weight percent is respectively 55-93%, 4-43%, 1-6%, it is characterized in that in emulsion polymerization, the 3-6% (following all with) that adds amount of monomer successively contains the compound emulsifying agent of amphoteric emulsifier, the 0.1-0.4% peroxide initiator, the 0.1-2% DDM dodecyl mercaptan, under the 45-75 ℃ of reaction conditions, vinyl cyanide and divinyl binary copolymerization make nitrile rubber; The emulsion pH value is controlled at 6.5-7, and under the temperature of reaction 65-70 ℃ of condition, adding contains the carboxyl unsaturated hydrocarbons, and the superoxide of content 0.5-1%, reacts to obtain micro mist shape suspension after 1-3 hour.
Purpose of the present invention can also reach by following measure:
Contain the carboxyl unsaturated hydrocarbons and adopt methyl methacrylate or MALEIC ANHYDRIDE.
Embodiment:
Embodiment 1.
Have in the polymeric kettle of chuck in the stirring of a withstand voltage 1.6MPa band, add soft water 400kg successively, 7-8% potassium stearate solution 300L, 2% ammonium persulfate solution 50L, DDM dodecyl mercaptan 2L, 2% Sodium dodecylbenzene sulfonate solution 50L, 3-5% Klorvess Liquid 50L adds vinyl cyanide 185L, adds soft water 100L again, with the air in the nitrogen replacement polymeric kettle, add divinyl 540L after oxygen level is lower than 0.2% in the analysis polymeric kettle.Stir intensification polymeric kettle temperature in 2 hours and reach 45 ℃, ladder-elevating temperature to 65 ℃ in 6 hours, transformation efficiency reaches 95%, after adding is dissolved with benzoyl peroxide 7.5-12g methyl methacrylate 7.5-12kg, 65-70 ℃ of reaction 2-3 hour, deliver to the flash drum vacuum with top discharge and slough unreacted monomer when the grafts transformation efficiency reaches 95%, deliver to degassing tower and further slough unreacted acrylonitrile, the suspension after the degassing advances the emulsion storage tank.Be little powdered suspension and be conveyed into the nodularization device with shurry pump, add phenol antioxidant (as 1076) simultaneously, particulate after the nodularization under agitation with separant such as silicone oil, calcium stearate, talcum powder, lime carbonate thorough mixing, then through centrifugal drying, cross behind 40 eye mesh screens this product.This product molecular weight is 31-32 ten thousand.
With polyvinyl chloride (PVC) 100g, dioctyl phthalate (DOP) (DOP) 50g, this product 10g, composite salt 5g, 170 ℃ of two roller plasticated.
Particular product performance parameters is as follows:
100% tensile modulus 637N/cm
3
Tensile strength 2180N/cm
3
Elongation at break 350%
-5 ℃ of low-temperature extensions 52%
Its diffuse reflectance infrared spectroscopy: characteristic peak is arranged, see Fig. 1 at-1728cm.
This product can be made the transparent PVC goods for giving the cross-linking type carboxyl acrylonitrile-butadiene rubber powder, as sebific duct, hard sheet, film etc.
Embodiment 2.
At a withstand voltage 1.6MPa, band stirs in the polymeric kettle that chuck is arranged and adds soft water 400kg successively, 6% potassium stearate solution 300L, 2% ammonium persulfate solution 45L, 2% lauryl sodium sulfate aqueous solution 30L, DDM dodecyl mercaptan 10L, 10% wet chemical 50L adds vinyl cyanide 250L, adds soft water 100L again, with the air in the nitrogen replacement polymeric kettle, analyze the interior oxygen level of polymeric kettle and be lower than 0.2% back adding divinyl 445L.Material temperature rise to 45 ℃ in stir heating up in 2 hours polymeric kettle, ladder-elevating temperature to 65 ℃ in 6 hours, reach at 95% o'clock at transformation efficiency and add 20% MALEIC ANHYDRIDE aqueous solution 70L, add 5% ammonium persulfate solution 3L simultaneously, keep 65-70 ℃ of reaction 1-2 hour, the grafts transformation efficiency reaches 95% with top discharge, is little powdered suspension and delivers to flash drum and slough unreacted monomer, and then deliver to degassing tower and further slough unreacted acrylonitrile, the suspension after the degassing advances the latex storage tank.Be micronized suspension and import the nodularization device with shurry pump, add phenol antioxidant (as 1076) simultaneously, rubber powder slurry after the nodularization in agitator with separant such as silicone oil, calcium stearate, talcum powder, lime carbonate thorough mixing after centrifugal drying cross 40 eye mesh screens and get this product.This product molecular weight is 8-9 ten thousand.
This product is used for polyvinyl chloride (PVC) flooring laminate by following prescription can make the thick random bending of PVC flooring laminate of 3mm and leakless, high resilience.
PVC100g, DOP60-80g, this product 5g, lime carbonate 300-500g, composite salt 5g.
Embodiment 3.
At a withstand voltage 1.6MPa, band stirs in the polymeric kettle that chuck is arranged and adds soft water 400kg successively, 8% potassium stearate solution 300L, 2% sodium lauryl sulphate 50L, 2% potassium persulfate solution 50L, DDM dodecyl mercaptan 3L, 5% Klorvess Liquid 50L adds vinyl cyanide 25L, add soft water 100L again, with air in the nitrogen replacement polymeric kettle, after oxygen level is lower than 0.2% in the analysis polymeric kettle, add divinyl 750L.Start and stir, in 2 hours with polymeric kettle in material temperature rise to 50 ℃, ladder-elevating temperature to 65 ℃ in 6 hours, transformation efficiency reaches at 95% o'clock and adds 20% maleic, two sour dissatisfied aqueous solution 80M and 5% ammonium persulfate solution 7L, keep 65-70 ℃ of reaction 1-2 hour, the grafts transformation efficiency reaches 95% with top discharge, is little powdered suspension and advances flash drum and remove unreacted monomer, advance degassing tower again and slough the intact vinyl cyanide of unreacted, the suspension after the degassing advances the emulsion storage tank.Be the outstanding suspension of little powdered and be conveyed into the nodularization device with shurry pump, add phenolic antioxidant (as 1076) simultaneously, micelle after the nodularization under agitation with separant such as silicone oil, talcum powder, lime carbonate thorough mixing, then through centrifugal drying, cross 40 eye mesh screens and get this product.
This product infrared spectra is seen Fig. 2, and Fig. 2 has characteristic peak at-1640cm.
This product is used for the toughness reinforcing of polyvinyl chloride (PVC) profiled material extruded product, low temperature resistant notch shock excellence by following prescription; Can be used for the modification of polyolefin resines such as polypropylene.
PVC100g, composite salt 7g, stearic acid 1g, this product 4g, lime carbonate 20g.
Particular product performance parameters is as follows:
Breach normal temperature shock strength 6.3KJ/m
2
Breach-10 ℃ shock strength 5.04KJ/m
2
Non-notch normal temperature shock strength 14.42KJ/m
2
Non-notch-10 ℃ shock strength 13.99KJ/m
2
Tensile strength 37MPa
The present invention has following advantage compared to existing technology:
1, this product is used for polyvinyl chloride (PVC), phenolic resins (PF), ABS, Merlon The resin toughenings such as resin (PC), polyamide (PA) are made anti-impact modifier, give simultaneously resin Low temperature resistantly subdue, the characteristic such as wear-resisting, oil resistant;
2, the powdery XNBR is convenient to mixed with resin evenly, can directly advance extruder processing;
3, improved the compatibility of resin, although molten Jie's degree parameter of acrylonitrile-butadiene rubber is close with PVC, but still Gap is arranged, introduce carboxyl gap is dwindled, use methyl methacrylate-grafted, can PVC transparent article processed, Colloform is cellular, light-permeable;
4, under agitation, its micelle is separated out into fine powder from the protective layer of micella, and carboxyl connects in suspended state Branch is to acrylonitrile-butadiene rubber, and its production cost is low, and equipment investment is few;
5, polymerisation conversion is high more than 95%, and the high dry powder 95% of fine powder rate is crossed 40 eye mesh screens;
6, this product can be used the single screw extrusion machine blend, is fit to medium and small sized enterprises and produces rubber and plastic alloy.
Claims (3)
1, a kind of preparation technology of carboxyl acrylonitrile-butadiene rubber powder, wherein the carboxy nitrile rubber component is divinyl, vinyl cyanide, contains the carboxyl unsaturated hydrocarbons, its weight percent is respectively 55-93%, 4-43%, 1-6%, it is characterized in that in emulsion polymerization, the 3-6% compound emulsifying agent that adds amount of monomer successively, 0.1-0.4% peroxide initiator, 0.1-2% DDM dodecyl mercaptan, under the 45-75 ℃ of reaction conditions, vinyl cyanide and divinyl binary copolymerization make nitrile rubber; Under the temperature of reaction 65-70 ℃ of condition, add and contain the carboxyl unsaturated hydrocarbons, and the superoxide of content 0.5-1%, the emulsion pH value is controlled at 6.5-7, reacts to obtain micro mist shape suspension after 1-3 hour.
2, the preparation technology of carboxyl acrylonitrile-butadiene rubber powder according to claim 1 is characterized in that containing the carboxyl unsaturated hydrocarbons and adopts MALEIC ANHYDRIDE.
3, the preparation technology of carboxyl acrylonitrile-butadiene rubber powder according to claim 1 is characterized in that compound emulsifying agent adopts potassium stearate and sodium lauryl sulphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107122A CN1058726C (en) | 1997-09-19 | 1997-09-19 | Carboxyl acrylonitrile-butadiene rubber powder and its prepn. tech. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107122A CN1058726C (en) | 1997-09-19 | 1997-09-19 | Carboxyl acrylonitrile-butadiene rubber powder and its prepn. tech. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1181390A CN1181390A (en) | 1998-05-13 |
| CN1058726C true CN1058726C (en) | 2000-11-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97107122A Expired - Fee Related CN1058726C (en) | 1997-09-19 | 1997-09-19 | Carboxyl acrylonitrile-butadiene rubber powder and its prepn. tech. |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9879158B2 (en) | 2011-05-31 | 2018-01-30 | Denka Company Limited | Primer composition and adhesive tape |
| CN106117746B (en) * | 2016-07-27 | 2018-07-17 | 联塑科技发展(贵阳)有限公司 | A kind of high density polyethylene (HDPE) plasticizing mother particle and preparation method thereof and its application in hdpe pipe |
| CN115043997B (en) * | 2021-03-08 | 2023-07-25 | 中国石油天然气股份有限公司 | A method for preparing carboxyl-containing thermoplastic elastomer by emulsion polymerization and the prepared thermoplastic elastomer |
| CN114920880A (en) * | 2022-06-10 | 2022-08-19 | 江苏亚泰化工有限公司 | Modified butyronitrile latex as well as preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6073221A (en) * | 1983-09-30 | 1985-04-25 | Hitachi Ltd | Dehumidifier structure |
| RU2074202C1 (en) * | 1992-05-26 | 1997-02-27 | Государственный научно-исследовательский институт химии и технологии полимеров им.акад.В.А.Каргина с опытным заводом | Method for production of modifying agent for polyvinyl chloride |
-
1997
- 1997-09-19 CN CN97107122A patent/CN1058726C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6073221A (en) * | 1983-09-30 | 1985-04-25 | Hitachi Ltd | Dehumidifier structure |
| RU2074202C1 (en) * | 1992-05-26 | 1997-02-27 | Государственный научно-исследовательский институт химии и технологии полимеров им.акад.В.А.Каргина с опытным заводом | Method for production of modifying agent for polyvinyl chloride |
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| Publication number | Publication date |
|---|---|
| CN1181390A (en) | 1998-05-13 |
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Assignee: Huangshan Hualan Technology Co., Ltd. Assignor: Qi Shengjie Contract record no.: 2011340000342 Denomination of invention: Carboxyl acrylonitrile-butadiene rubber powder and its prepn. tech. Granted publication date: 20001122 License type: Exclusive License Open date: 19980513 Record date: 20110815 |
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