CN1508170A - Method for preparing thermoplastic cross-linked rubber - Google Patents
Method for preparing thermoplastic cross-linked rubber Download PDFInfo
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- CN1508170A CN1508170A CNA021567395A CN02156739A CN1508170A CN 1508170 A CN1508170 A CN 1508170A CN A021567395 A CNA021567395 A CN A021567395A CN 02156739 A CN02156739 A CN 02156739A CN 1508170 A CN1508170 A CN 1508170A
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Abstract
The invention is a dynamic-all-vulcanization method to prepare thermoplastic vulcanized rubber. The operating steps: (1) premixing rubber and plastic according to a certain proportion; (2) preparing mother rubber by mix-refining the left rubber, the filling, the softening agent, the aging agent and the processing assistant; (3) dynamically vulcanizing to the premixed substance, the mother rubber, the vulcanizing agent and the accelerant; (4) late charging-oil to obtain it.
Description
Technical field the present invention relates to the method that a kind of dynamic full vulcanization technology prepares thermoplastic sulfurized rubber, preparing the new preparation process that proposes on the original prescription of the thermoplastic sulfurized rubber basis with melt-blending process, this method can prepare the thermoplastic sulfurized rubber of high workability, low compression deformation, soft.
Background technology dynamic full vulcanization technology is to sneak into rubber in the thermoplastic resin matrix, with linking agent mixing the time, can make rubber " on the spot " produce chemically crosslinked fully, and under high-speed mixing and shearing action, crosslinked rubber is fractured into the great quantity of micron particle, be dispersed among the successive thermoplastic resin matrix, thereby form thermoplastic elastic glue (being called for short TPV).The selectable rubber of preparation TPV has usually: terpolymer EP rubber, isoprene-isobutylene rubber, trans-isoprene, natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), ethylene-vinyl acetate copolymer, acrylic elastomer, chlorinated polyethylene rubber, chloroprene rubber, paracril or their mixture.Thermoplastic resin matrix's plastics have polypropylene, polyethylene, polystyrene, acrylonitrile-butadiene-styrene terpolymer, styrene-acrylonitrile copolymer, polymethylmethacrylate, polybutylene terephthalate, nylon, polycarbonate or their mixture usually.Can prepare rubber and plastic than from 90/10～10/90 thermoplastic sulfurized rubber with the dynamic full vulcanization technology, full sulfuration is meant that the rubber that the cross-linking density of rubber is at least 7 * 10-5mol/mL or 97% is crosslinked.TPV not only has the excellent comprehensive performance, and has a processing characteristics of thermoplastic material, replace traditional rubber in a lot of fields just gradually, thermoplastic sulfurized rubber is high speed development why, its major cause is the machine-shaping advantage that it has thermoplastics, and with heat cured rubber phase ratio, production efficiency is higher, and recyclable use repeatedly, and under the not too high situation of use temperature requirement, has the elastic performance that compares favourably with cross-linked rubber.As far back as the beginning of the eighties, just having with EPDM/polypropylene thermoplastic cross-linked rubber (EPDM/PP TPV) abroad is typical suitability for industrialized production.
The typical preparation method of TPV is: earlier plastics are dropped into fusion in advance in the high-temperature mixer, again rubber is added and be mixed together, and then add auxiliary agent successively, filler and tenderizer mix, add vulcanizing agent and promotor at last and carry out dynamic vulcanization, in " Thermoplastic vulcanizates ofolefin rubber and polyolefin resin " (U.S. Pat 4130535), " Thermoplastic elastomeric blends of olefin rubber and polyolefinresin " (U.S. Pat 4311628) and " Dynamically vulcanized alloyshaving two copolymers in the erosslinked phase and a crystallinematrix " (U.S. Pat 5073597) all has report.The all basic performance of setting about improving the blended thermoplastic gonosome from the composition of raw materials aspect of the research in relevant this field both at home and abroad.U.S. Advanced Elastomer Systems, L.P. [AES.Co.] discloses a kind of in the presence of a kind of vulcanization system in " thermoplatic elastomer vulcanizate " (Chinese patent application number 98108434.6), by the thermoplatic elastomer vulcanizate of dynamic vulcanization from a kind of thermoplastic terpolymer and a kind of rubber constituent and a kind of non-essential additive preparation, this thermoplastic elastic vulcanized rubber has superior physicals, have excellent processing characteristics again, terpolymer accounts at least a propylene that contains of 10%～70% weight of composition gross weight in the thermoplastic copolymer of this invention, ethene and a kind of thermoplastic terpolymer that contains the alpha-olefin of 4 carbon atoms at least.The said firm " polypropylene thermoplastic elastomer compositions " (Chinese patent application number 99807124.2) with higher processing characteristics and physical property balance disclose adopt polypropene composition melt flow rate (MFR) about 0.5 to about 5 decigrams/minute scope, and its molecular weight distribution mw/mn is from greater than 5.5 to the highest about 20, and prepared thermoplastic sulfurized rubber has the processing characteristics of raising when keeping good physicals." Thermoplastic vulcanizates from isobutylene rubber and eitherEPDM or a conjugated diene rubber " (U.S. Pat 5,621,045) discloses in order to improve the over-all properties of TPV, the patent application of tertiary blending has been proposed, two kinds of rubber constituents are arranged in this blend, as the combination of isobutene rubber and ethylene-propylene rubber(EPR) or natural rubber, tertiary blending helps improving the over-all properties of blend.
(Polym.Mater.sci.Eng 1998 at " Kinetic Model of DynamicVulcanization " for the preparation technology of blending type thermoplastic cross-linked rubber, 79 102-103) in the summary paper introduction is arranged, preparation technology can be classified as two classes substantially, the first kind is a melt-blending process, and such also is a technology of preparing modal, that be applied to suitability for industrialized production at present abroad.This technology of preparing mainly contains two kinds of concrete technologies, the difference of these two kinds of technologies is the adding mode of vulcanizing agent, a kind of is that vulcanizing agent adds behind rubber and plastics and uniform mixing such as filler and tenderizer, another kind is that vulcanizing agent, filler and tenderizer etc. are pre-applied in the rubber, and then is mixed into the sulfuration of action attitude with plastics.Second class is a solution polymerization process, and is also at the experimental stage at present.
As everyone knows, to a certain extent, dynamic vulcanization technology is not the thermoplastic sulfurized rubber that is well suited for preparing the soft high workability, because soft TPV generally obtains by improving rubber phase content, a large amount of elastomerics particles easily forms network structure, along with rubber content improves, the elasticity of material increases, and prepared material becomes and is difficult to extrude, even can not realize extruding processing.The key that influences the blending type thermoplastic cured properties is the control method and the means of morphological structure and rubber phase particle diameter.Because contain a large amount of cross-linked rubber particles among the TPV, these rubber particles easily form network structure, thereby influence the flowability of TPV.If reduce the content of rubber phase, then mobile can the raising, but the hardness of TPV and compression set also can increase, i.e. flexibility decrease.Therefore exist contradiction between the elasticity of TPV and the flowability, the high elastomeric TPV that flows of preparation is a difficult point always.Traditional way generally is by changing prescription or adopting more advanced processing units to solve this problem.
Summary of the invention the present invention is intended to propose a kind of thermoplastic sulfurized rubber prescription with routine prepares thermoplastic sulfurized rubber in the processing units of routine method, and this method can prepare the thermoplastic sulfurized rubber of high workability, low compression deformation, soft.
It is earlier with plastics fusion in advance and rubber mix that traditional melt-blending process prepares thermoplastic sulfurized rubber, adds auxiliary agent, filler, tenderizer again and mixes, and adds vulcanizing agent and promotor at last and carries out dynamic vulcanization.The preparation method's that the present invention proposes operation steps is as follows:
(1) rubber and plastics premix: earlier with part rubber and plastics premix, the rubber total amount that participates in premix accounts for the 20-60% of rubber gross weight in the thermoplastic elastomer that will prepare;
(2) preparation of rubber rubber master batch: become rubber master batch with remaining rubber and filler, tenderizer, aging agent, processing aid are mixing;
(3) dynamic vulcanization: will go up the rubber and plastic of two step preparations and plastics pre-composition and rubber rubber master batch and vulcanizing agent, promotor and carry out dynamic vulcanization;
(4) later stage is oil-filled: add 10～40% oil of plastics weight content, continue to mix, promptly obtain the blending type thermoplastic cross-linked rubber.
The used rubber of the present invention is known thermoplastic sulfurized rubber rubber commonly used, for example: trans-isoprene, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), ethylene-vinyl acetate copolymer, acrylic elastomer, chlorinated polyethylene rubber, chloroprene rubber, paracril or their mixture.The used plastics of the present invention are known thermoplastic sulfurized rubber plastics commonly used, for example: polystyrene, acrylonitrile-butadiene-styrene terpolymer, styrene-acrylonitrile copolymer, polymethylmethacrylate, polybutylene terephthalate, nylon, polycarbonate or their mixture.
Oil-filled used oil of later stage of the present invention is known thermoplastic sulfurized rubber oil commonly used, for example: naphthenic oil, paraffin oil, Vaseline or their mixture.The tenderizer that oil-filled used oil product kind of later stage and known thermoplastic sulfurized rubber are commonly used is identical or different.
The present invention mainly adopts two technology: the one, and part rubber and plastics premix; The 2nd, the dynamic vulcanization later stage is filled a certain amount of oil tech.
It is very even that rubber and plastic premix technology makes that the rubber of plastics and part is pre-mixed, further add rubber after, all rubber and plastics will form even phase in the short period of time.Because whole dynamic vulcanization process is very short, so this technology can avoid in the traditional dynamic vulcanization technology rubber and plastic can not the uniform disadvantage of thorough mixing effectively, also avoided some traditional method to have a mind to prolong the pre-mixing time in order to increase the rubber and plastic mixture homogeneity, and caused filler and various Synergist S-421 95s to plastics mutually in the shortcomings of a large amount of migrations.The uniform mixing of rubber plastic is crucial for successfully realizing phase reversion in next step dynamic vulcanization process and obtaining the tiny particle that is evenly coated mutually by plastics, and tiny rubber particles also is indispensable for high workability and the snappiness of TPV.
The oil-filled technology in back is meant in the dynamic vulcanization later stage and adds the oil that accounts for the 20%-40% that is equivalent to plastic content again that this part oil can carry out, also can be directly oil-filled to finished product TPV after dynamic vulcanization is finished.Like this, oil can small part can infiltrate in the rubber grain, major part can stay plastics mutually in.Experiment showed, as long as the oil and the plastics that are charged into have enough consistencies, and consumption exceeds, can obviously reduce hardness and the compression set of TPV, and can improve flowability.Its reason is by reaching the compression set that reduces TPV and improve mobile purpose with the plasticising and the increase-volume of plastics molecule mutually.
The used prescription of the present invention is existing, known thermoplastic sulfurized rubber prescription, on the basis of the conventional equipment that does not change original prescription and use (mill, Banbury mixer or screw extrusion press), proposes new preparation method.
Except that for the existing known rubber and plastics that is usually used in, other filler, auxiliary agent are also used always, tenderizer for example: naphthenic oil, paraffin oil or Vaseline etc.; Filler is for example: white carbon black, carbon black, tripoli, potter's clay etc.; Vulcanizing agent is for example: organo-peroxide, sulphur, resol etc.; Other auxiliary agents are for example: stearic acid, oxidation inhibitor etc.
All properties test of the present invention is all according to corresponding national standards, can obviously find out from embodiments of the invention and corresponding Comparative Examples, adopt the performance of the prepared thermoplastic sulfurized rubber of technology of preparing of the present invention and comparing by the conventional art preparation, the thermoplastic elastic glue of the technology of the present invention preparation aspect compression set and hardness all well below the prepared cross-linked rubber of traditional technological method, other mechanical properties are maintained substantially, flowability can be significantly improved, compression set (elasticity of reflection cross-linked rubber) can reduce about 8%～10%, hardness can reduce by 5～10 shore As, and mechanical property can be maintained basically.
Description of drawings Fig. 1 is the instron flow curve figure of the thermoplastic elastic glue of the embodiment of the invention and Comparative Examples preparation.
Embodiment is listed in the performance of the thermoplastic elastic glue of the embodiment of the invention and Comparative Examples preparation in the table 1.
Embodiment 1 preparation rubber and plastic than be isoprene-isobutylene rubber/polypropylene (IIR/PP) thermoplastic sulfurized rubber of 60/40 (rubber of participation premix accounts for 40% of whole rubber weight, the later stage is oil-filled account for plastics weight 20%).Operation steps is as follows:
1) antioxidant 1010 with 48 gram isoprene-isobutylene rubbers and 80 gram acrylic plastering and 0.8 gram mixes in 170 ℃ twin-roll plasticator, and is about 3 minutes, standby.
The 72 gram isoprene-isobutylene rubbers that 2) will be left drop into the normal temperature mill, mix up suitable roll spacing, press the compounding process of rubber, repeatedly add 1.2 gram stearic acid successively on a small quantity, the white carbon black of 48 grams, play 6 triangle bags, add 120 grams again and, play 6 triangle bags with oily (naphthenic oil and Vaseline, and with weight ratio 1: 1), make the rubber rubber master batch, standby.
3) rubber and plastic pre-composition, the rubber rubber master batch that will go up the preparation of two steps drops into 180 ℃ of twin-roll plastic mixing mills successively, and roll spacing 0.5mm after 30 seconds, adds 14.2 gram uncle octyl phenol urea formaldehydes, mixes 30 seconds, adds 2.8 gram tin protochlorides at last and carries out dynamic vulcanization 15 minutes.
4) add 16 grams and with oil (naphthenic oil and Vaseline, and with weight ratio 1: 1), continue mixing until evenly, promptly obtain rubber and plastic than the IIR/PP blending type thermoplastic cross-linked rubber that is 60/40.Performance sees Table 1 and Fig. 1.
Embodiment 2 preparation rubber and plastics than be 80/20 EPT rubber (EPDM/PP) thermoplastic sulfurized rubber (rubber of participation premix accounts for 60% of whole rubber weight, the later stage is oil-filled account for plastics weight 10%).Operation steps is as follows:
1) restrain terpolymer EP rubbers and 40 gram acrylic plastering and 0.4 gram antioxidant 1010 with 64 and in 170 ℃ mixing tank, mix, about 3 minutes, standby.
The 96 gram terpolymer EP rubbers that 2) will be left drop into the normal temperature mill, mix up suitable roll spacing, press the compounding process of rubber, repeatedly add 1.6 gram stearic acid successively on a small quantity, the white carbon black of 64 grams is played 6 triangle bags, adds 160 gram naphthenic oils again, play 6 triangle bags, make the rubber rubber master batch, standby.
3) rubber and plastic pre-composition, the rubber rubber master batch that will go up the preparation of two steps drops into 180 ℃ of twin-roll plastic mixing mills successively, and roll spacing 0.5mm after 30 seconds, adds 4.8 gram organo-peroxide DCP, carries out dynamic vulcanization 8 minutes.
4) add the naphthenic oils of 4 grams, continue to mix until evenly.Promptly obtain rubber and plastic than the EPDM/PP blending type thermoplastic cross-linked rubber that is 80/20.Performance sees Table 1 and Fig. 1.
(rubber that participates in premix accounts for 20% of whole rubber weight to embodiment 3 preparation rubber and plastics than natural rubber/polyethylene (NR/PE) thermoplastic sulfurized rubber that is 70/30, oil-filled 40% of the plastics weight that accounts for of later stage, oil-filled kind of later stage is different with the tenderizer kind in second step).Operation steps is as follows:
1) antioxidant 1010 with 28 gram natural rubbers and 60 gram vinyons and 0.6 gram mixes in 170 ℃ mixing tank, and is about 3 minutes, standby;
The 112 gram natural rubbers that 2) will be left drop into the normal temperature mill, mix up suitable roll spacing, press the compounding process of rubber, repeatedly add the stearic acid of 1.4 grams successively on a small quantity, the white carbon black of 56 grams is played 6 triangle bags, adds 140 gram paraffin oils again, play 6 triangle bags, make the rubber rubber master batch, standby;
3) rubber and plastic pre-composition, the rubber rubber master batch that will go up the preparation of two steps drops into 180 ℃ of twin-roll plastic mixing mills successively, and roll spacing 0.5mm after 30 seconds, adds 14.0 gram uncle octyl phenol urea formaldehydes, mixes 30 seconds, adds 2.8 gram tin protochlorides at last and carries out dynamic vulcanization 15 minutes;
4) add 24 grams and with oil (naphthenic oil and Vaseline, and with weight ratio 1: 1), continue mixing until evenly.Promptly obtain rubber and plastic than the NR/PE blending type thermoplastic cross-linked rubber that is 70/30.Performance sees Table 1 and Fig. 1.From the performance table as seen, even change oil-filled kind of later stage, so long as the cross-linked rubber by the technology of the present invention preparation, just can reach the purpose of high workability low compression deformation soft.
Comparative Examples 1 usefulness conventional dynamic sulfurization technology prepares rubber and plastic than the IIR/PP thermoplastic sulfurized rubber (composition of prescription and consumption are with example 1) that is 60/40.Operation steps is as follows:
1) butyl plastics and the antioxidant 1010 with whole consumptions drops into 170 ℃ twin-roll plasticator, until plasticizing evenly, and about 2 minutes.
2) again the isoprene-isobutylene rubber of whole consumptions is dropped in the plastics that the first step plastifies, be mixed to evenly.
3) after the rubber and plastic of previous step mixes, repeatedly add white carbon black successively in batches on a small quantity and and use oily.Until mixing.Roll spacing furnishing 0.5mm, add uncle's octyl phenol urea formaldehyde again, mixed 30 seconds, add tin protochloride at last and carried out dynamic vulcanization 15 minutes.
Performance sees Table 1 and Fig. 1.From table 1 and Fig. 1 as seen, the cross-linked rubber of conventional art preparation is in elasticity, and aspects such as mobile and hardness all are not so good as the cross-linked rubber that the technology of the present invention prepares.
Comparative Examples 2 rubber and plastic premixs, do not carry out oil-filled preparation rubber and plastic of later stage than the IIR/PP thermoplastic sulfurized rubber that is 60/40 (with the difference of embodiment 1 be finish the 3rd step dynamic vulcanization after, it is oil-filled not carry out the later stage).Performance sees Table 1 and Fig. 1.From table 1 and Fig. 1 as seen, implement oil-filled technology of later stage, can largely improve the elasticity of cross-linked rubber, reduce the hardness of cross-linked rubber, but mechanical properties of vulcanizate is reduced.
Comparative Examples 3 rubber and plastics are premix not, and oil-filled technology of later stage prepares rubber and plastic than the IIR/PP thermoplastic sulfurized rubber (composition of prescription and consumption are with embodiment 1) that is 60/40.Operation steps is as follows: earlier carry out dynamic vulcanization with the traditional preparation process technology of Comparative Examples 1, it is oil-filled to adopt the oil-filled technology of embodiment 1 to carry out the later stage then) performance sees Table 1 and Fig. 1.From table 1 and Fig. 1 as seen, only can improve mechanical property and elasticity to a certain extent, but can not reduce the hardness of cross-linked rubber with rubber and plastic premix technology.
Comparative Examples 4 conventional dynamic sulfurization technologies prepare rubber and plastic than the EPDM/PP thermoplastic sulfurized rubber that is 80/20 (composition of prescription and consumption are with embodiment 2, and technology of preparing is with Comparative Examples 1).Performance sees Table 1 and Fig. 1.
Comparative Examples 5 conventional dynamic sulfurization technologies prepare rubber and plastic than the NR/PE thermoplastic sulfurized rubber that is 80/20 (composition of prescription and consumption are with example 3, and technology of preparing is with Comparative Examples 1).Performance sees Table 1 and Fig. 1.
Table 1
| Hardness (Shao A) | 100% stretches (MPa) surely | Tensile strength (MPa) | Elongation (%) | Tear strength (KN/m) | Tensile set (%) | 100 ℃ * 22h of compression set (%) | The Instron rheometer is extruded the kapillary sample appearance | |
| Embodiment 1 | ????65 | ????3.2 | ????11.0 | ????400 | ????33.5 | ????26 | ????35.6 | Smooth |
| Embodiment 2 | ????49 | ????1.8 | ????7.0 | ????330 | ????20.0 | ????16 | ????23.0 | Smooth |
| Embodiment 3 | ????55 | ????2.0 | ????9.1 | ????340 | ????26.0 | ????16 | ????25.1 | Smooth |
| Comparative Examples 1 | ????71 | ????3.8 | ????10.1 | ????376 | ????28.0 | ????26 | ????45.0 | Smooth |
| Comparative Examples 2 | ????70 | ????3.8 | ????11.5 | ????400 | ????32.0 | ????26 | ????40.0 | Smooth |
| Comparative Examples 3 | ????65 | ????3.2 | ????9.0 | ????330 | ????29.0 | ????25 | ????38.5 | Smooth |
| Comparative Examples 4 | ????54 | ????2.0 | ????7.5 | ????340 | ????20.0 | ????16 | ????32.0 | Coarse |
| Comparative Examples 5 | ????60 | ????2.5 | ????9.8 | ????380 | ????30.1 | ????20 | ????32.0 | Smooth |
Claims (5)
1. the preparation method of a thermoplastic sulfurized rubber, first with melt-blending process with plastics fusion in advance and rubber mix, add auxiliary agent, filler, tenderizer again and mix, add vulcanizing agent and promotor at last and carry out dynamic vulcanization, it is characterized in that operation steps is as follows:
(1) rubber and plastics premix: earlier with part rubber and plastics premix, the rubber total amount that participates in premix accounts for the 20-60% of rubber gross weight in the thermoplastic elastomer that will prepare;
(2) preparation of rubber rubber master batch: become rubber master batch with remaining rubber and filler, tenderizer, aging agent, processing aid are mixing;
(3) dynamic vulcanization: will go up the rubber and plastic of two step preparations and plastics pre-composition and rubber rubber master batch and vulcanizing agent, promotor and carry out dynamic vulcanization;
(4) later stage is oil-filled: add 10～40% oil of plastics weight content, continue to mix, promptly obtain the blending type thermoplastic cross-linked rubber.
2. the preparation method of thermoplastic sulfurized rubber according to claim 1, it is characterized in that: rubber is trans-isoprene, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), ethylene-vinyl acetate copolymer, acrylic elastomer, chlorinated polyethylene rubber, chloroprene rubber, paracril or their mixture.
3. the preparation method of thermoplastic sulfurized rubber according to claim 1, it is characterized in that: plastics are polystyrene, acrylonitrile-butadiene-styrene terpolymer, styrene-acrylonitrile copolymer, polymethylmethacrylate, polybutylene terephthalate, nylon, polycarbonate or their mixture.
4. the preparation method of thermoplastic sulfurized rubber according to claim 1, it is characterized in that: the later stage, oil-filled used oil was naphthenic oil, paraffin oil, Vaseline or their mixture.
5. the preparation method of thermoplastic sulfurized rubber according to claim 4, it is characterized in that: the later stage, oil-filled used oil product kind and tenderizer were identical or different.
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| CN100400573C (en) * | 2005-06-20 | 2008-07-09 | 北京化工大学 | Flame-retardant thermoplastic sulfurized rubber preparation method |
| CN100400574C (en) * | 2006-09-12 | 2008-07-09 | 北京化工大学 | Method for raising fluidity of thermoplastic cross-linked rubber |
| CN103012875A (en) * | 2012-12-20 | 2013-04-03 | 青岛科技大学 | Trans-polyisoprene/polypropylene thermoplastic vulcanized rubber |
| CN103589126A (en) * | 2013-11-28 | 2014-02-19 | 青岛科技大学 | Nitrile rubber/polylactic acid thermoplastic vulcanizate and preparation method |
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| CN111100342A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Rubber toughened plastic and preparation method thereof |
| CN111484684A (en) * | 2020-06-04 | 2020-08-04 | 青岛科技大学 | High-damping low-odor environment-friendly butyl rubber/polypropylene thermoplastic vulcanized rubber and preparation method thereof |
| CN111748136A (en) * | 2020-07-06 | 2020-10-09 | 安徽中鼎橡塑制品有限公司 | Thermoplastic vulcanized elastomer for wire harness sheath and preparation method thereof |
| CN112870657A (en) * | 2021-02-03 | 2021-06-01 | 天长市正牧铝业科技有限公司 | PU (polyurethane) leather basketball based on high-elasticity rubber outer skin and preparation process thereof |
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