CN1821301A - Sulfurizing system and chlorinated isobutylene rubber/polyolefine thermoplastic elastomer - Google Patents
Sulfurizing system and chlorinated isobutylene rubber/polyolefine thermoplastic elastomer Download PDFInfo
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- CN1821301A CN1821301A CN 200610023512 CN200610023512A CN1821301A CN 1821301 A CN1821301 A CN 1821301A CN 200610023512 CN200610023512 CN 200610023512 CN 200610023512 A CN200610023512 A CN 200610023512A CN 1821301 A CN1821301 A CN 1821301A
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- thermoplastic elastomer
- isobutylene rubber
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- polyolefine
- chlorinated isobutylene
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Abstract
The present invention discloses a kind of sulfurizing system and chlorinated isobutylene rubber/polyolefin thermoplastic elastomer. The sulfurizing system includes sulfurizing agent, catalyst and activator, and the sulfurizing agent as sulfur donor may be used to replace sulfur, is easy to disperse and safe. The sulfurizing glue comprising the sulfurizing agent, ZnO and/or MgO has cross-linking bond with low sulfur content, excellent mechanical performance, heat resistance, ageing resistance, and less permanent compression deformation. The chlorinated isobutylene rubber/polyolefin thermoplastic elastomer prepared through dynamic sulfurizing technology has great tensile strength, great extension at break up to 600 %, less compression deformation and other advantages, may be used in producing wire, cable, heat resisting product, etc.
Description
Technical field
The present invention relates to a kind of chlorinated isobutylene rubber/polyolefine thermoplastic elastomer, more specifically relate to the vulcanization system for preparing chlorinated isobutylene rubber/polyolefine thermoplastic elastomer.
Background technology
Thermoplastic elastomer is a development in recent years ratio type material faster.Microcosmic phase structure with the blending thermoplastic elastomer (TPV) of dynamic vulcanization technology preparation is that cross-linked rubber is evenly dispersed in the plastic substrate with the micron order size as disperse phase, be not only tool tradition caoutchouc elasticity but also the resilient material that can process with thermoplastic plastics shaping equipment of a class, thereby in a lot of fields, obtaining using widely.
In the blending thermoplastic elastomer of dynamic vulcanization technology preparation, the EPDM/PP thermoplastic sulfurized rubber is commercialization the earliest and studies maximum dynamic vulcanization thermoplastic elastomers both at home and abroad.In recent years, both at home and abroad the dynamic vulcanization thermoplastic elastomer to other co-mixing system has carried out development research, the patent even the product of the thermoplastic elastomer of systems such as NBR/PP, NBR/PVC, EPDM/PA occurred comprising.But butyl rubber/Thermoplastic Elastomer, Olefinic, the particularly less appearance of chlorinated isobutylene rubber/polyolefine thermoplastic elastomer body.The isobutylene rubber/polyolefine dynamic vulcanization thermoplastic elastomer patent (U.S.Pat.No.4,130,534) of U.S. Monsanto Company application is mainly non-halogenated isoprene-isobutylene rubber; Belgium Exxon company has applied for that " the dynamic vulcanization alloy of crystal type polyolefine and halogenated butyl rubber " patent (U.S.Pat.No.5,021,500) is mainly brominated butyl rubber.
But there is an obvious defects in the technology of above-mentioned Patent publish, and the elasticity of its product is relatively poor, and elongation is not high, can not be used for the medical package goods, as medical embolism etc.Present medical embolism mainly uses isoprene-isobutylene rubber or halogenated butyl rubber, particulate that the rubber plug may bring and extractum can cause medicine pollution to a certain degree, can influence medicine purity when serious, and employing is the forming process mode of traditional vulcanization of rubber glue, thereby shaping speed is slow, production efficiency is low, the production cost height.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of vulcanization system and chlorinated isobutylene rubber/polyolefine thermoplastic elastomer, to overcome the above-mentioned defective that prior art exists.
Chlorinated isobutylene rubber/polyolefine thermoplastic elastomer body of the present invention is the feedstock production that comprises following component and parts by weight:
100 parts of chlorinated butyl rubbers
50～70 parts of polyolefine
50～90 parts of non-reinforced fillings
1～10 part of vulcanizing agent
1～3 part of catalyzer
3～9 parts in activator
Described polyolefine is selected from polyethylene or polypropylene, and polypropylene comprises alfon or propylene copolymer, preferred propylene copolymer;
Described non-reinforced filling comprises calcinated argil, lime carbonate, talcum powder or kaolin, and non-reinforced filling is preferably calcinated argil.
Vulcanizing agent, catalyzer and activator are formed described vulcanization system;
Described vulcanizing agent is selected from sulphur, tert butyl phenolic resin, zinc diethyldithiocarbamate (ZDEDC) or curing-N, N '-dicaprolactam, and preferred curing-N, the N-dicaprolactam, curing-N, N-dicaprolactam molecular formula is:
Curing-N, N-dicaprolactam are the commercially available prod, and TUV company produces, and product grade is Rhenocure S.
Described catalyzer is selected from SnCl
2Or ZnCl
2, preferred ZnCl
2
Described activator is selected from ZnO or/and MgO, preferably ZnO.ZnO can also play the effect of vulcanizing agent in chlorinated butyl rubber.
The preferred vulcanizing agent of the present invention is a sulfur donor, can partly or entirely substitute Sulfur, easily disperses operational safety.The present invention add ZnO with this vulcanizing agent or/and MgO to make the cross-link bond sulphur content of cross-linked rubber lower, have the good mechanical performance, heat-resisting, ageing-resistant, compression set is little.Be applicable to and make electric wire, cable, heat-resisting goods, thick product and medical embolism;
For processing and the use properties that improves material, also comprise 6～10 parts of auxiliary agents in the thermoplastic elastomer of the present invention, auxiliary agent comprise tenderizer or/and lubricant or/and promotor or/and oxidation inhibitor;
Described tenderizer can be selected from paraffin oil;
Described lubricant can be selected from stearic acid, solid paraffin or polyethylene wax;
Described promotor is selected from the mixture of tetramethyl-thiuram disulfide (TMTD) and curing dibenzo plug azoles (DM), the part by weight of tetramethyl-thiuram disulfide and curing dibenzo plug azoles is: tetramethyl-thiuram disulfide: curing dibenzo plug azoles=1: 1～3, preferred 1: 2;
Described oxidation inhibitor can be selected from oxidation inhibitor [four (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (claiming antioxidant 1010 again).
Described auxiliary agent is the processing aid of this area routine, all can adopt commercially available commercially produced product.
The present invention preferably adopts the feedstock production of following component and parts by weight:
100 parts of chlorinated butyl rubbers, 50～70 parts of propylene copolymers, curing-N, 5 parts of N '-dicaprolactam, ZnCl
21～3 part, 1 part of MgO, 3～9 parts of ZnO, 1～1.5 part of antioxidant 1010,2～4 parts of paraffin oils, 1 part of tetramethyl-thiuram disulfide, 2 parts of curing dibenzo plug azoles; 50～90 parts of calcinated argils.
The preparation method of chlorinated isobutylene rubber/polyolefine thermoplastic elastomer body of the present invention comprises the steps:
(1) with chlorinated butyl rubber, non-reinforced filling in rubber mixing machine, under 40～50 ℃ of temperature, mixing 10～12 minutes, obtains rubber unvulcanizate;
(2) in the Banbury of Haake torque rheometer Banbury mixer, rotor speed is 60～90rpm, blending temperature is under 170～190 ℃ of conditions, add polyolefine and auxiliary agent, plasticizing 1～10min adds the rubber unvulcanizate that step (1) makes then, blend 2～4min, add vulcanizing agent, catalyzer and auxiliary agent, sulfuration blend 4～8min obtains the chlorinated isobutylene rubber/polyolefine thermoplastic elastomer body.
Said auxiliary agent also can add in step (1), or adds respectively in step (1) and step (2).
The present invention adopts novel vulcanization system, chlorinated butyl rubber/Co-polypropylene the thermoplastic elastomer that adopts the dynamic vulcanization blending technology to make, compare with other halogenated butyl rubber/Thermoplastic Elastomer, Olefinic and to have following advantage: tensile strength is big, elongation at break is big, can reach more than 600%, compression set is little.The present invention compares with the chlorinated butyl rubber cross-linked rubber, has the working method that forming process can adopt thermoplastics, does not need sulfuration, save energy, productivity advantages of higher.Can replace chlorinated butyl rubber application in some aspects, on medical embolism.
Embodiment
With some examples the specific implementation method that the present invention uses is described below, material therefor is as follows:
Chlorinated butyl rubber: Exxon CIIR 1066, Exxon chemical company;
Calcinated argil: commercially available;
Paraffin oil: Sunpar 2080, commercially available;
Processing aid: paraffin, polyethylene wax, stearic acid is commercially available;
ZnO, ZnCl
2, MgO, TM monex TD, altax is commercially available;
Curing-N, N '-dicaprolactam: Rhenocure S, Rhein produces;
Propylene copolymer, alfon, linear low density polyethylene: commercially available;
Antioxidant 1010: commercially available.
Embodiment 1
Thermoplastic elastomer according to 5 chlorinated isobutylene rubber/polyolefines of the preparation of the basic recipe shown in the table 1.
(1) at first in two roll rubber mixing mill in 40 ℃ with chlorinated butyl rubber and calcinated argil, paraffin oil, MgO carries out mixing, obtains mixing rubber master batch;
(2) then in the Banbury of Haake torque rheometer Banbury mixer, at 180 ℃, under the rotor speed 65rpm condition, add propylene copolymer and antioxidant 1010, plasticizing 2min adds mixing rubber master batch blend 3min, adds ZnO, ZnCl
2, TM monex TD, altax, curing-N, N '-dicaprolactam carries out dynamic vulcanization blend 7min, and blend is pressed into sheet.
Tensile strength, 100% tensile modulus, 300% tensile modulus, elongation at break, tensile set is measured according to GB528-92, and compression set is measured according to GB/T7759-1996.
The thermoplastic elastomer that prescription according to table 1 is made carries out the test of tensile property, hardness, aging resistance, and test result is listed in table 2.
Table 1
| Raw material | Weight part |
| Chlorinated scoline calcinated argil paraffin oil stearic acid low-molecular polyethylene wax paraffin ZnO ZnCl2TM monex TD altax MgO curing-N, N '-dicaprolactam propylene copolymer antioxidant 1010 | 100 50 3111 specify (seeing Table 2) 11215 42.9 2 specially |
Table 2
| Specimen coding | 1 | 2 | 3 | 4 | 5 |
| ZnO add-on (Phr) | 3 | 4 | 5 | 7 | 9 |
| Cured properties | |||||
| 100% surely stretch (MPa) 300% surely stretch (MPa) hot strength (MPa) elongation at break (%) tensile set (%) compression set (%) (100 ℃, 24h) hardness (Shao Shi) swelling ratio (%) gel content (%) | 3.9 5.9 7.7 465.5 88 6.3 83 212.5 80.4 | 4.0 6.5 8.0 465.5 68 7.4 81 203.1 86.2 | 4.4 7.0 8.3 617.9 72 6.3 82 189.0 87.3 | 4.2 6.5 8.0 483.0 76 8.1 83 202.5 87.6 | 4.2 6.4 7.4 489.3 68 7.8 84 208.9 88 |
| Aging resistance (120 ℃, 72h) | |||||
| 100% stretches (MPa) 300% surely stretches (MPa) tensile strength (MPa) elongation at break (%) surely | 3.4 4.9 7.6 367.0 | 3.8 5.8 7.7 382.3 | 3.9 6.0 8.0 428.0 | 3.8 5.6 7.8 424.9 | 3.6 5.3 7.7 396.7 |
Embodiment 2
According to embodiment 1 described processing method, press the thermoplastic elastomer of 5 chlorinated isobutylene rubber/polyolefines of formulation of table 3.Test tensile property, hardness, aging resistance, test result such as table 4.
Table 3
| Raw material | Weight part |
| Chlorinated scoline calcinated argil paraffin oil stearic acid low-molecular polyethylene wax paraffin ZnO ZnCl2TM monex TD altax | 100 50 31115 specify (seeing Table 4) 12 specially |
| MgO curing-N, N '-dicaprolactam propylene copolymer antioxidant 1010 | 1 5 42.9 2 |
Table 4
| Specimen coding | 1 | 2 | 3 | 4 | 5 |
| ZnCl 2Add-on (Phr) | 0 | 0.5 | 1 | 2 | 3 |
| Cured properties | |||||
| 100% surely stretch (MPa) 300% surely stretch (MPa) hot strength (MPa) elongation at break (%) tensile set (%) compression set (%) (100 ℃, 24h) hardness (Shao Shi) swelling ratio (%) gel content (%) | 4.2 6.5 7.8 465.5 80 8.3 85 217.4 80.0 | 3.9 6.3 7.5 437.0 68 4.8 84 201.3 85.7 | 4.4 7.0 8.3 617.9 72 6.3 82 189 87.3 | 4.1 6.5 8.1 463.3 68 4.8 84 186.2 87.8 | 4.1 6.4 7.1 422.6 68 5.6 83 184.6 88.2 |
| Aging resistance (120 ℃, 72h) | |||||
| 100% stretches (MPa) 300% surely stretches (MPa) tensile strength (MPa) elongation at break (%) surely | 3.6 5.1 7.6 386.5 | 3.7 5.7 7.3 369.2 | 3.9 6.0 8.0 428.0 | 3.9 6.0 7.4 363.5 | 3.9 5.9 7.6 382.7 |
Embodiment 3
According to embodiment 1 described processing method, press the thermoplastic elastomer of 6 chlorinated isobutylene rubber/polyolefines of formulation of table 5.Test tensile property, hardness, aging resistance, test result such as table 6.
Table 5
| Raw material | Weight part |
| Chlorinated butyl rubber | 100 |
| Calcinated argil paraffin oil stearic acid low-molecular polyethylene wax paraffin ZnO ZnCl 2TM monex TD altax MgO curing-N, N '-dicaprolactam propylene copolymer antioxidant 1010 | 50 311151121 specify (seeing Table 6) 42.9 2 specially |
Table 6
| Specimen coding | 1 | 2 | 3 | 4 | 5 | 6 |
| N, N '-curing dicaprolactam add-on (Phr) | 0 | 1 | 3 | 5 | 7 | 9 |
| Cured properties | ||||||
| 100% surely stretch (MPa) 300% surely stretch (MPa) hot strength (MPa) elongation at break (%) tensile set (%) compression set (%) (100 ℃, 24h) hardness (Shao Shi) | 3.1 4.7 4.9 386.5 68 5.2 76 | 3.5 5.7 6.2 369.2 71 5.3 85 | 3.5 5.7 7.2 428.0 69 4.8 84 | 4.4 7.0 8.3 617.9 72 6.3 82 | 3.3 5.5 6.7 396.1 78 4.8 84 | 3.1 5.0 5.4 327.9 68 5.6 83 |
| Aging resistance (120 ℃ of 72h) | ||||||
| 100% stretches (MPa) 300% surely stretches (MPa) tensile strength (MPa) elongation at break (%) surely | 2.4 4.2 4.5 309.0 | 2.7 4.9 5.3 327.4 | 2.8 4.8 6.7 387.4 | 3.9 6.0 8.0 428.0 | 3.0 4.6 6.0 382.7 | 2.9 4.3 4.3 302.3 |
Embodiment 4
According to embodiment 1 described processing method, press the thermoplastic elastomer of 3 chlorinated isobutylene rubber/polyolefines of formulation of table 7.Test tensile property, hardness, test result such as table 8.
Table 7
| Raw material | Weight part | ||
| Chlorinated scoline calcinated argil paraffin oil stearic acid low-molecular polyethylene wax paraffin ZnO ZnCl2Vulcanization accelerator TMTD altax MgO curing-N, N '-dicaprolactam propylene copolymer Noblen LLDPE age resistor 1010 | 100 50 3 1 1 1 5 1 1 2 1 5 42.9 / / 2 | 100 50 3 1 1 1 5 1 1 2 1 5 / 42.9 / 2 | 100 50 3 1 1 1 5 1 1 2 1 5 / / 42.9 2 |
Table 8
| Polyolefine | Propylene copolymer | Alfon | Linear low density polyethylene |
| 100% stretches (MPa) 300% surely stretches (MPa) tensile strength (MPa) elongation at break (%) tensile set (%) hardness (Shao Shi) surely | 4.4 7.0 8.3 617.9 72 82 | 5.2 7.5 7.8 336.0 68 86 | 2.6 3.94 6.50 484.0 102 69 |
Although according to description of the invention, vulcanization system prescription and technology have reached best mode and embodiment, and the present invention does not limit to therewith, but in the scope of described claim.
Claims (10)
1. a vulcanization system comprises vulcanizing agent, catalyzer and activator, and its parts by weight are;
1～10 part of vulcanizing agent
1～3 part of catalyzer
3～9 parts in activator
Said vulcanizing agent is selected from sulphur, tert butyl phenolic resin, zinc diethyldithiocarbamate (ZDEDC) or curing-N, N '-dicaprolactam, and said catalyzer is selected from SnCl
2Or ZnCl
2Said activator is selected from ZnO or/and MgO.
2. vulcanization system according to claim 1 is characterized in that vulcanizing agent is selected from curing-N, N-two lactan, and said catalyzer is selected from ZnCl
2, said activator is selected from ZnO.
3. a chlorinated isobutylene rubber/polyolefine thermoplastic elastomer body is characterized in that, is to adopt the vulcanization system of claim 1 to prepare, and the component and the parts by weight of raw material comprise:
100 parts of chlorinated butyl rubbers
50～70 parts of polyolefine
50～90 parts of non-reinforced fillings
1～10 part of vulcanizing agent
1～3 part of catalyzer
3～9 parts in activator.
4. chlorinated isobutylene rubber/polyolefine thermoplastic elastomer body according to claim 3 is characterized in that described polyolefine is selected from polyethylene or polypropylene.
5. chlorinated isobutylene rubber/polyolefine thermoplastic elastomer body according to claim 4 is characterized in that polypropylene is selected from alfon or propylene copolymer.
6. chlorinated isobutylene rubber/polyolefine thermoplastic elastomer body according to claim 3 is characterized in that, said non-reinforced filling comprises calcinated argil, lime carbonate, talcum powder or kaolin.
7. chlorinated isobutylene rubber/polyolefine thermoplastic elastomer body according to claim 6 is characterized in that, non-reinforced filling is a calcinated argil.
8. according to each described chlorinated isobutylene rubber/polyolefine thermoplastic elastomer body of claim 3～7, it is characterized in that, also comprise 6～10 parts of auxiliary agents, auxiliary agent comprise tenderizer or/and lubricant or/and promotor or/and oxidation inhibitor.
9. chlorinated isobutylene rubber/polyolefine thermoplastic elastomer body according to claim 8 is characterized in that said tenderizer can be selected from paraffin oil; Said lubricant can be selected from stearic acid, solid paraffin or polyethylene wax; Said promotor is selected from the mixture of tetramethyl-thiuram disulfide and curing dibenzo plug azoles, and said oxidation inhibitor is selected from [four (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
10. chlorinated isobutylene rubber/polyolefine thermoplastic elastomer body according to claim 9, it is characterized in that the part by weight of tetramethyl-thiuram disulfide and curing dibenzo plug azoles is: tetramethyl-thiuram disulfide: curing dibenzo plug azoles=1: 1～3.
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| CN1026239C (en) * | 1991-10-30 | 1994-10-19 | 北京化工学院 | Thermoplastic ethylene-propylene rubber/polyolefine elastomer and its prepn. |
| US5290886A (en) * | 1993-04-20 | 1994-03-01 | Advanced Elastomer Systems, L.P. | Thermoplastic elastomers having improved low temperature properties |
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