CN108409891A - A kind of chlorinated rubber preparation method - Google Patents
A kind of chlorinated rubber preparation method Download PDFInfo
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- CN108409891A CN108409891A CN201810296777.5A CN201810296777A CN108409891A CN 108409891 A CN108409891 A CN 108409891A CN 201810296777 A CN201810296777 A CN 201810296777A CN 108409891 A CN108409891 A CN 108409891A
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- chlorinated rubber
- rubber preparation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/12—Incorporating halogen atoms into the molecule
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- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of chlorinated rubber preparation methods, are related to technical field of rubber production, including the synthesis of chlorinating agent t-butyl hypochlorate, chlorination reaction, and 3 steps of post-processing, wherein introduce ultraviolet radiation in chlorination reaction.Chlorinated rubber preparation method using the present invention is reduced into production cost, and production equipment is simple, improves chlorination efficiency, chlorinity is up to 68%, and technical indicator complies fully with requirement.
Description
Technical field
The present invention relates to technical field of rubber production, and in particular to a kind of chlorinated rubber preparation method.
Background technology
Chlorinated rubber is modified through chlorination reaction as raw material using natural rubber or synthetic rubber.Has excellent film forming
Property, adhesiveness, wearability, anti-corrosion property and quick-drying outstanding and water proofing property, be a kind of important coating raw material, belong to rubber and derive
Product it is compacted can to improve product hardness and wearability, confrontation with natural or a variety of synthetic resin and rubber blending in most cases
It is critically important to become coating, adhesive that performance has higher requirements.
Chlorinating agent used in existing chlorinated rubber production technology is chlorine, production equipment is required it is high, safety compared with
It is low.Using liquid chlorine agent alternatively, reducing into production cost, and production equipment is simple.The present invention then explores new chlorination rubber
Compose technique.
Invention content
Problem to be solved by this invention is to provide a kind of chlorinated rubber preparation method of simple production process.
To achieve the goals above, the technical solution that the present invention takes is：
(1) t-butyl hypochlorate synthesizes, and the three-necked flask equipped with condenser pipe, blender is placed in ice-water bath, is first added
Liquor natrii hypochloritis opens stirring, waits for that temperature drops to 0 DEG C, then sequentially add the tert-butyl alcohol and glacial acetic acid.After complete reaction,
It is first washed with 10% sodium carbonate liquor, neutralizes unreacted glacial acetic acid, then be washed with deionized three times, washed away unreacted
Raw material.T-butyl hypochlorate product is packed into after being dried with anhydrous calcium chloride to be filled the brown reagent bottle of anhydrous calcium chloride and is placed in refrigerator
Middle preservation.
(2) chlorination reaction dilutes the original gelatin of butadiene rubber with chloroform, and the butadiene rubber solution after dilution is added to
It in there-necked flask, stirs, be heated to 60 DEG C, monochloroacetic acid is added.70 DEG C are warming up to, t-butyl hypochlorate is added dropwise, is aided with ultraviolet light
The reaction was continued for radiation.
(3) it post-processes, the rubber solutions after reaction are washed with deionized, stand, separate water phase under strong agitation.Split-phase
Rubber liquid afterwards is slowly injected into the absolute ethyl alcohol that anti-aging agent is added and washes out, and the chlorinated polybutadiene after precipitation is done in vacuum
It is dried to get to finished product in dry case.
Sodium hypochlorite and tert-butyl alcohol molar ratio are 1.2-1.6 in step (1):1, preferably 1.4:1.
Butadiene rubber solution content in step (2) after dilution is 2-5% (quality), preferably 3%.
T-butyl hypochlorate time for adding is 1.5-3h, preferably 2h in step (2).
The a length of 280-400nm of ultraviolet light wave, preferably 300nm in step (2).
Anti-aging agent is MB, one kind in MBZ, NBC, preferably MB in step (3).
Vacuum drying condition is 35 DEG C in step (3), and vacuum degree is less than 133Pa.
Specific implementation mode
Embodiment 1
Three-necked flask equipped with condenser pipe, blender is placed in ice-water bath, liquor natrii hypochloritis is first added, unlatching is stirred
It mixes, waits for that temperature drops to 0 DEG C, then sequentially add the tert-butyl alcohol and glacial acetic acid, wherein sodium hypochlorite and tert-butyl alcohol molar ratio are 1.4:
1.After complete reaction, it is first washed with 10% sodium carbonate liquor, neutralizes unreacted glacial acetic acid, then be washed with deionized three
It is secondary, wash away unreacted raw material.It is packed into after being dried with anhydrous calcium chloride and fills the brown reagent bottle of anhydrous calcium chloride and be placed in refrigerator
Middle preservation.
The original gelatin of butadiene rubber is diluted with chloroform, butadiene rubber content is 3% (quality), by the suitable fourth rubber after dilution
Sol solution is added in there-necked flask, is stirred, is heated to 60 DEG C, monochloroacetic acid is added.70 DEG C are warming up to, the tertiary fourth of hypochlorous acid is added dropwise
Ester, time for adding 2h.It is aided with ultraviolet radiation, a length of 300nm of ultraviolet light wave, the reaction was continued.
Rubber solutions after reaction are washed with deionized, stand, separate water phase under strong agitation.Rubber liquid after split-phase
It is slowly injected into the absolute ethyl alcohol that antioxidant MB is added and washes out, the chlorinated polybutadiene after precipitation is dried in vacuum drying chamber
Dry vacuum drying condition is 35 DEG C, and vacuum degree is less than 133Pa, and finished product chlorinity is 68%.
Embodiment 2
Three-necked flask equipped with condenser pipe, blender is placed in ice-water bath, liquor natrii hypochloritis is first added, unlatching is stirred
It mixes, waits for that temperature drops to 0 DEG C, then sequentially add the tert-butyl alcohol and glacial acetic acid, wherein sodium hypochlorite and tert-butyl alcohol molar ratio are 1.2:
1.After complete reaction, it is first washed with 10% sodium carbonate liquor, neutralizes unreacted glacial acetic acid, then be washed with deionized three
It is secondary, wash away unreacted raw material.It is packed into after being dried with anhydrous calcium chloride and fills the brown reagent bottle of anhydrous calcium chloride and be placed in refrigerator
Middle preservation.
The original gelatin of butadiene rubber is diluted with chloroform, butadiene rubber content is 2.5% (quality), by the suitable fourth after dilution
Rubber solutions are added in there-necked flask, are stirred, are heated to 60 DEG C, monochloroacetic acid is added.70 DEG C are warming up to, the tertiary fourth of hypochlorous acid is added dropwise
Ester, time for adding 1.5h.It is aided with ultraviolet radiation, a length of 280nm of ultraviolet light wave, the reaction was continued.
Rubber solutions after reaction are washed with deionized, stand, separate water phase under strong agitation.Rubber liquid after split-phase
It is slowly injected into the absolute ethyl alcohol that antioxidant MB Z is added and washes out, by the chlorinated polybutadiene after precipitation in vacuum drying chamber
It is 35 DEG C to dry vacuum drying condition, and vacuum degree is less than 133Pa, and finished product chlorinity is 65%.
Embodiment 3
Three-necked flask equipped with condenser pipe, blender is placed in ice-water bath, liquor natrii hypochloritis is first added, unlatching is stirred
It mixes, waits for that temperature drops to 0 DEG C, then sequentially add the tert-butyl alcohol and glacial acetic acid, wherein sodium hypochlorite and tert-butyl alcohol molar ratio are 1.6:
1.After complete reaction, it is first washed with 10% sodium carbonate liquor, neutralizes unreacted glacial acetic acid, then be washed with deionized three
It is secondary, wash away unreacted raw material.It is packed into after being dried with anhydrous calcium chloride and fills the brown reagent bottle of anhydrous calcium chloride and be placed in refrigerator
Middle preservation.
The original gelatin of butadiene rubber is diluted with chloroform, butadiene rubber content is 5% (quality), by the suitable fourth rubber after dilution
Sol solution is added in there-necked flask, is stirred, is heated to 60 DEG C, monochloroacetic acid is added.70 DEG C are warming up to, the tertiary fourth of hypochlorous acid is added dropwise
Ester, t-butyl hypochlorate time for adding are 3h.It is aided with a length of 400nm of ultraviolet radiation ultraviolet light wave, the reaction was continued.
Rubber solutions after reaction are washed with deionized, stand, separate water phase under strong agitation.Rubber liquid after split-phase
It is slowly injected into the absolute ethyl alcohol that antioxidant NBC is added and washes out, by the chlorinated polybutadiene after precipitation in vacuum drying chamber
It is 35 DEG C to dry vacuum drying condition, and vacuum degree is less than 133Pa, and finished product chlorinity is 62%.
Embodiment 4
Three-necked flask equipped with condenser pipe, blender is placed in ice-water bath, liquor natrii hypochloritis is first added, unlatching is stirred
It mixes, waits for that temperature drops to 0 DEG C, then sequentially add the tert-butyl alcohol and glacial acetic acid, wherein sodium hypochlorite and tert-butyl alcohol molar ratio are 1.4:
1.After complete reaction, it is first washed with 10% sodium carbonate liquor, neutralizes unreacted glacial acetic acid, then be washed with deionized three
It is secondary, wash away unreacted raw material.It is packed into after being dried with anhydrous calcium chloride and fills the brown reagent bottle of anhydrous calcium chloride and be placed in refrigerator
Middle preservation.
The original gelatin of butadiene rubber is diluted with chloroform, content is 3% (quality), and the butadiene rubber solution after dilution is added
Enter into there-necked flask, stirs, is heated to 60 DEG C, monochloroacetic acid is added.It is warming up to 70 DEG C, is added dropwise t-butyl hypochlorate, when dropwise addition
Between be 2h.It is aided with a length of 280nm of ultraviolet radiation ultraviolet light wave, the reaction was continued.
Rubber solutions after reaction are washed with deionized, stand, separate water phase under strong agitation.Rubber liquid after split-phase
It is slowly injected into the absolute ethyl alcohol that antioxidant MB is added and washes out, the chlorinated polybutadiene after precipitation is dried in vacuum drying chamber
Dry vacuum drying condition is 35 DEG C, and vacuum degree is less than 133Pa, and finished product chlorinity is 60%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (7)
1. a kind of chlorinated rubber preparation method, which is characterized in that including following processing steps：
(1) t-butyl hypochlorate synthesizes, and the three-necked flask equipped with condenser pipe, blender is placed in ice-water bath, and time chlorine is first added
Acid sodium solution opens stirring, waits for that temperature drops to 0 DEG C, then sequentially add the tert-butyl alcohol and glacial acetic acid.After complete reaction, it first uses
10% sodium carbonate liquor washing, neutralizes unreacted glacial acetic acid, then be washed with deionized three times, washes away unreacted original
Material, t-butyl hypochlorate product is fitted into after being dried with anhydrous calcium chloride to be filled the brown reagent bottle of anhydrous calcium chloride and is placed in refrigerator
It preserves；
(2) chlorination reaction dilutes the original gelatin of butadiene rubber with chloroform, and the butadiene rubber solution after dilution is added to three mouthfuls
It in bottle, stirs, be heated to 60 DEG C, monochloroacetic acid is added.70 DEG C are warming up to, t-butyl hypochlorate is added dropwise, is aided with ultraviolet radiation
The reaction was continued；
(3) it post-processes, the rubber solutions after reaction are washed with deionized, stand under strong agitation, separate water phase, after split-phase
Rubber liquid is slowly injected into the absolute ethyl alcohol that anti-aging agent is added and washes out, by the chlorinated polybutadiene after precipitation in vacuum drying chamber
Middle drying is to get to finished product.
2. chlorinated rubber preparation method as described in claim 1, it is characterised in that：In the step (1) sodium hypochlorite with
Tert-butyl alcohol molar ratio is 1.2-1.6:1.
3. chlorinated rubber preparation method as described in claim 1, it is characterised in that：It is suitable after dilution in the step (2)
Buna solution content is 2-5% (quality).
4. chlorinated rubber preparation method as described in claim 1, it is characterised in that：The tertiary fourth of hypochlorous acid in the step (2)
Ester time for adding is 1.5-3h.
5. chlorinated rubber preparation method as described in claim 1, it is characterised in that：Ultraviolet wavelength in the step (2)
For 280-400nm.
6. chlorinated rubber preparation method as described in claim 1, it is characterised in that：Anti-aging agent is MB in the step (3),
One kind in MBZ, NBC.
7. chlorinated rubber preparation method as described in claim 1, it is characterised in that：Vacuum drying item in the step (3)
Part is 35 DEG C, and vacuum degree is less than 133Pa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810296777.5A CN108409891A (en) | 2018-04-04 | 2018-04-04 | A kind of chlorinated rubber preparation method |
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| CN201810296777.5A CN108409891A (en) | 2018-04-04 | 2018-04-04 | A kind of chlorinated rubber preparation method |
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| CN108409891A true CN108409891A (en) | 2018-08-17 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5473024A (en) * | 1993-10-05 | 1995-12-05 | University Of Southern Mississippi | Synthesis and coating application of chlorinated hydroxyrubber |
| CN101280028A (en) * | 2008-05-23 | 2008-10-08 | 童柏林 | Non-carbon tetrachloride waterless type green production method of chlorinated rubber |
| CN102268107A (en) * | 2011-08-26 | 2011-12-07 | 福建万泰兴化工发展有限公司 | Chlorinated rubber and production method thereof |
| US20120319062A1 (en) * | 2011-06-15 | 2012-12-20 | Lion Copolymer, Llc | Fire retardant brominated rubber polymeric composition and method for making |
| CN104530264A (en) * | 2014-12-30 | 2015-04-22 | 安徽微威胶件集团有限公司 | Preparation method for producing chlorinated rubber |
| CN106397642A (en) * | 2015-07-29 | 2017-02-15 | 瑞来斯实业公司 | A process for chlorination of a polymer |
-
2018
- 2018-04-04 CN CN201810296777.5A patent/CN108409891A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5473024A (en) * | 1993-10-05 | 1995-12-05 | University Of Southern Mississippi | Synthesis and coating application of chlorinated hydroxyrubber |
| CN101280028A (en) * | 2008-05-23 | 2008-10-08 | 童柏林 | Non-carbon tetrachloride waterless type green production method of chlorinated rubber |
| US20120319062A1 (en) * | 2011-06-15 | 2012-12-20 | Lion Copolymer, Llc | Fire retardant brominated rubber polymeric composition and method for making |
| CN102268107A (en) * | 2011-08-26 | 2011-12-07 | 福建万泰兴化工发展有限公司 | Chlorinated rubber and production method thereof |
| CN104530264A (en) * | 2014-12-30 | 2015-04-22 | 安徽微威胶件集团有限公司 | Preparation method for producing chlorinated rubber |
| CN106397642A (en) * | 2015-07-29 | 2017-02-15 | 瑞来斯实业公司 | A process for chlorination of a polymer |
Non-Patent Citations (2)
| Title |
|---|
| 夏宇正等: "顺丁橡胶的氯化及其氯含量的控制", 《合成橡胶工业》 * |
| 李艳丽等: "新型橡胶氯化剂的合成与表征", 《北京化工大学学报》 * |
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Application publication date: 20180817 |