CN1421465A - Prepn process of high-hydroscopicity rubber - Google Patents
Prepn process of high-hydroscopicity rubber Download PDFInfo
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- CN1421465A CN1421465A CN 02151279 CN02151279A CN1421465A CN 1421465 A CN1421465 A CN 1421465A CN 02151279 CN02151279 CN 02151279 CN 02151279 A CN02151279 A CN 02151279A CN 1421465 A CN1421465 A CN 1421465A
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Abstract
The present invention is the preparation process of high-hydroscopicity rubber. In a mixer and at certain mixing temperature, metal hydroxide and unsaturated carboxylic acid are added into rubber to in-situ product metal salt of unsaturated carboxylic acid and the rubber is vulcanized through adding peroxide in plate vulcanizing machine at certain vulcanizing condition so as to produce high-hydroscopicity rubber modified with metal salt of unsaturated carboxylic acid. The modified rubber has good hydroscopic expanding performance and excellent mechanical performance. The product may be used in waterproof and leak-stopping jobs for various building engineering.
Description
Technical field: the present invention relates to a kind of preparation method of functional high molecule material, particularly a kind of preparation method of high suction type rubber.
Background technology: well-known, in the molecule of rubber substrate, introduce the component that has the group of hydrophile function or in rubber substrate, add possess hydrophilic property, just can give rubber with the water-swelling function.Water swelling rubber was come out the seventies in 20th century, and as far back as Japanology and developed rapidly, the U.S., Germany, France, Britain and China have also carried out research in depth subsequently.Mitsubishi changes into Co., Ltd. (day disclosure special permission communique, flat 09-137015,1977) and makes the water swelling rubber with excellent machinability with chlorinatedpolyethylene and starch grafted acrylate blend.Japan catalyst chemical company (day disclosure special permission communique, flat 01-141979,1989; Day disclosure special permission communique, flat 09-40837,1997) make water-absorbing resin with nonionic monomers (acrylamide) and anionic monomer (sodium acrylate) earlier, make water swelling rubber with blend rubber then.Kuraray company (water-absorbing Rubber Composition[P] .EP55848) with polydiene with make water swelling rubber with epoxy crosslinked water-absorbing resin blend.C I kasei company (day disclosure special permission communique, clear 53-24455,1978; US4211851,1978; Ger273774,1978) use iso-butylene-copolymer-maleic anhydride, polyoxyethylene glycol, ethylene-acrylic acid vinyl ester copolymers to form water-retaining agent, rubber is distributed to the moulding that dewaters after the blend in the above-mentioned water-retaining agent emulsion makes water swelling rubber.Units such as China Chengdu Univ. of Science ﹠ Technology, Jilin University, Beijing University of Chemical Technology, Hubei University and academy of sciences's Guangzhou chemistry institute, Jiangsu chemical institute are all studied Water Swelling Rubber Made by Blending.In sum, all be to adopt earlier synthetic water-absorbing resin, then itself and blend rubber are prepared water swelling rubber.Because dispersion and the consistency of water-absorbing resin in rubber is difficult to guarantee, so adopt the material water-swelling and the physical and mechanical properties instability of this method preparation.Although can adopt suitable blend compatibilizing method to improve, complex process, cost height.If adopt the chemical graft method that the water-absorbent group is grafted on the rubber molecular chain, just can make the water swelling rubber of stable performance, but there is the graft reaction difficulty in chemical graft process, complex process is loaded down with trivial details, expansion rate of water absorption is low, so the research work of this respect is reported seldom.The physical blending method is extensive because of raw material sources, preparation is simple, and the water absorbent rate height of material, initial suction are widely studied and applied rapidly.
Summary of the invention: the objective of the invention is to overcome that existing Water Swelling Rubber Made by Blending unstable properties, water-absorbing resin are difficult to disperse, separate out easily,, repeatedly absorb water shortcomings such as after rate decline, poor processability and cost height poor with the consistency of rubber in rubber from rubber.The present invention mainly adopts original position to generate the operational path of acrylate metal salt, and a kind of method for preparing high suction type rubber is provided, and makes that material property is stable, suitability is strong, and satisfy that production technique is simple, good processability, requirement such as with low cost.
High suction type rubber of the present invention is in Banbury mixer or mill, under certain melting temperature, mixing with carrying out in metal hydroxides, unsaturated carboxylic acid, the organo-peroxide adding rubber successively, adopt vulcanizing press under suitable cure conditions, to vulcanize then, make the poly-in-situ modified water swelling rubber of metallic salts of unsaturated carboxylate.During preparation, organo-peroxide decomposes crosslinked on the spot, the polymerization and partially grafted to rubber macromolecule of initiation metallic salts of unsaturated carboxylate.The metallic salts of unsaturated carboxylate branch of the polymerization in situ simultaneously nano level divided particles that coordinates has improved dispersiveness and the consistency of metallic salts of unsaturated carboxylate in rubber, thereby has made high suction type rubber.
The preparation method of the high suction type of the present invention rubber is in Banbury mixer or mill, add rubber, sodium hydroxide, vinylformic acid, organo-peroxide successively, under 30～100 ℃ of temperature, carried out mixing 5～60 minutes, wherein rubber consumption is 100 weight parts, sodium hydroxide concentration is 2～30 weight parts, the vinylformic acid consumption is 5～60 weight parts, amount of peroxide is 0.3～8 weight part, under 140～200 ℃ of temperature, in vulcanizing press, vulcanized 3～60 minutes then, obtain the poly-in-situ modified height suction type rubber of metallic salts of unsaturated carboxylate.
The described rubber of preparation method of the high suction type of the present invention rubber is chlorinated polyethylene rubber, styrene-butadiene rubber(SBR), natural rubber, terpolymer EP rubber.
The described organo-peroxide of preparation method of the high suction type of the present invention rubber is dicumyl peroxide (DCP), dibenzoyl peroxide (BPO), ditertiary butyl peroxide (DBPH), 2,5-dimethyl-2,5-di-t-butyl peroxide hexane (DTBPH).
Height suction type rubber physical mechanical property, water-swelling property, process industrial art performance that the present invention makes are good, can be used for waterproof and the sealing leak stopping and the water pipe head sealing of civil construction projects such as railway, highway, city underground, building construction.The method of the high suction type of preparation provided by the invention rubber, technology is simple, easy to operate, with low cost to have excellent industrial application foreground.
Embodiment: the following examples are to further specify of the present invention, rather than limit the scope of the invention.
Implement 1～5: original position generates the high suction type rubber of sodium acrylate modified chlorinated polyethylene rubber (CPE) preparation
Under 50 ℃～60 ℃ temperature, earlier CPE is added Banbury mixer, then NaOH, AA, DCP are added rubber successively, mixing 15 minutes.According to 175 ℃ * 10 minutes cure conditions, the gained rubber unvulcanizate is become the thick test piece of 2mm with fluid pressure type flat plate heat vulcanizer molded vulcanization again.Sulfuration sample hardness is according to standard GB/T531 test, and tensile strength and tensile yield are tested according to standard GB/T528.
Expansion rate of water absorption test: specimen size is 20 * 20 * 2 (mm), and during test sample being weighed is soaked in the deionized water, takes out in different time and weighs, and must blot specimen surface moisture when weighing at every turn.The calculation formula of expansion rate of water absorption is as follows:
Sample weight * 100% before expansion rate of water absorption=suction back sample weight/suction
Prescription and test result such as table 1.
Embodiment 6～7: original position generates the high suction type rubber of sodium acrylate modified styrene butadiene rubber (SBR) preparation
Under 50 ℃～60 ℃ temperature, earlier SBR is added Banbury mixer, then NaOH, AA, DBPH or DCP are added rubber successively, mixing 15 minutes.According to 175 ℃ * 10 minutes cure conditions, the gained rubber unvulcanizate is become the thick test piece of 2mm with fluid pressure type flat plate heat vulcanizer molded vulcanization again.Sulfuration sample performance testing method is identical with embodiment 1～5.
Prescription and test result such as table 2.
Embodiment 8～9: original position generates the high suction type rubber of sodium acrylate modified natural rubber (NR) preparation
Under 50 ℃～60 ℃ temperature, earlier NR is added Banbury mixer, then NaOH, AA, DBPH or DCP are added rubber successively, mixing 15 minutes.According to 175 ℃ * 10 minutes cure conditions, the gained rubber unvulcanizate is become the thick test piece of 2mm with fluid pressure type flat plate heat vulcanizer molded vulcanization again.Sulfuration sample performance testing method is identical with embodiment 1～5.
Prescription and test result such as table 2.
Embodiment 10～11: original position generates the high suction type rubber of sodium acrylate modified EPT rubber (EPDM) preparation
Under 50 ℃～60 ℃ temperature, earlier EPDM is added Banbury mixer, then NaOH, AA, DBPH or DCP are added rubber successively, mixing 15 minutes.According to 175 ℃ * 10 minutes cure conditions, the gained rubber unvulcanizate is become the thick test piece of 2mm with fluid pressure type flat plate heat vulcanizer molded vulcanization again.Sulfuration sample performance testing method is identical with embodiment 1～5.Prescription and test result such as table 2.
Table 1
Example 12345 prescriptions (weight part)
CPE 100 100 100 100 100
NaOH 20 14 14 14 14
AA 36 26 26 26 26
DCP 1.0 0.5 1.5 2.0 2.5 physical and mechanical propertiess
Hardness, Shao Er A 81 80 83 86 86
Tensile strength, MPa 19.2 26.4 35.6 30.3 29.7
Tensile yield, % 312 293 236 174 140
Expansion rate of water absorption (maximum), physical and mechanical properties during % 135.6 161.2 191.8 190.4 205.3 water-swelling balances
Hardness, Shao Er A 50 55 45 42 52
Tensile strength, MPa 6.87 8.12 7.20 5.93 5.56
Tensile yield, % 380 304 261 215 167
Table 2
Example 6789 10 11 prescriptions (weight part)
SBR 100 100
NR 100 100
EPDM 100 100
NaOH 20 20 20 20 20 20
AA 36 36 36 36 36 36
DBPH 0.5 0.5 0.5
DCP 0.5 0.5 0.5 physical and mechanical propertiess
Hardness, Shao Er A 84 75 44 43 70 68
Tensile strength, MPa 13.3 14.1 8.36 8.98 9.25 12.6
Tensile yield, % 114 303 346 374 212 487
Expansion rate of water absorption (maximum), the physical mechanical energy during % 117.6 128.1 282.7 275.6 220.7 262.3 water-swelling balances
Hardness, Shao Er A 44 42 23 21 37 35 tensile strengths, MPa 8.26 8.74 4.36 4.75 6.73 7.64 tensile yield, % 296 383 642 660 394 542
Claims (3)
1. the preparation method of high suction type rubber, it is characterized in that in Banbury mixer or mill, add rubber, sodium hydroxide, vinylformic acid, organo-peroxide successively, under 30～100 ℃ of temperature, carried out mixing 5～60 minutes, wherein rubber consumption is 100 weight parts, sodium hydroxide concentration is 2～30 weight parts, the vinylformic acid consumption is 5～60 weight parts, amount of peroxide is 0.3～8 weight part, under 140～200 ℃ of temperature, in vulcanizing press, vulcanized 3～60 minutes then, obtain the poly-in-situ modified height suction type rubber of metallic salts of unsaturated carboxylate.
2. the preparation method of high suction type rubber according to claim 1 is characterized in that described rubber is chlorinated polyethylene rubber, styrene-butadiene rubber(SBR), natural rubber, terpolymer EP rubber.
3. the preparation method of high suction type rubber according to claim 1 is characterized in that organo-peroxide is dicumyl peroxide, dibenzoyl peroxide, ditertiary butyl peroxide, 2,5-dimethyl-2,5-di-t-butyl peroxide hexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02151279 CN1200022C (en) | 2002-12-12 | 2002-12-12 | Prepn process of high-hydroscopicity rubber |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02151279 CN1200022C (en) | 2002-12-12 | 2002-12-12 | Prepn process of high-hydroscopicity rubber |
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| CN1421465A true CN1421465A (en) | 2003-06-04 |
| CN1200022C CN1200022C (en) | 2005-05-04 |
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| CN 02151279 Expired - Fee Related CN1200022C (en) | 2002-12-12 | 2002-12-12 | Prepn process of high-hydroscopicity rubber |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331903C (en) * | 2005-04-12 | 2007-08-15 | 南京师范大学 | Method for synthesizing high water absorption resin from rubber powder |
| CN101717532B (en) * | 2009-12-04 | 2011-11-09 | 北京化工大学 | Method for preparing rubber water absorbent composite material comprising starch |
| CN102875700A (en) * | 2012-10-12 | 2013-01-16 | 武汉工程大学 | Method for modifying rubber base of water swelling nitrile rubber |
| CN103570878A (en) * | 2013-11-22 | 2014-02-12 | 江苏恒峰线缆有限公司 | High-strength ethylene propylene diene monomer and preparation method thereof |
| CN107652462A (en) * | 2017-08-31 | 2018-02-02 | 航天材料及工艺研究所 | A kind of hot energy-storage system and preparation method thereof |
-
2002
- 2002-12-12 CN CN 02151279 patent/CN1200022C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331903C (en) * | 2005-04-12 | 2007-08-15 | 南京师范大学 | Method for synthesizing high water absorption resin from rubber powder |
| CN101717532B (en) * | 2009-12-04 | 2011-11-09 | 北京化工大学 | Method for preparing rubber water absorbent composite material comprising starch |
| CN102875700A (en) * | 2012-10-12 | 2013-01-16 | 武汉工程大学 | Method for modifying rubber base of water swelling nitrile rubber |
| CN102875700B (en) * | 2012-10-12 | 2014-04-09 | 武汉工程大学 | Method for modifying rubber base of water swelling nitrile rubber |
| CN103570878A (en) * | 2013-11-22 | 2014-02-12 | 江苏恒峰线缆有限公司 | High-strength ethylene propylene diene monomer and preparation method thereof |
| CN103570878B (en) * | 2013-11-22 | 2016-01-06 | 江苏恒峰线缆有限公司 | A kind of High-strength ethylene propylene diene monomer and preparation method thereof |
| CN107652462A (en) * | 2017-08-31 | 2018-02-02 | 航天材料及工艺研究所 | A kind of hot energy-storage system and preparation method thereof |
| CN107652462B (en) * | 2017-08-31 | 2020-09-18 | 航天材料及工艺研究所 | Heat energy storage system and preparation method thereof |
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| CN1200022C (en) | 2005-05-04 |
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