CN1233703C - Method for preparing high-cohesiveness thermoplastic cross-linked rubber - Google Patents
Method for preparing high-cohesiveness thermoplastic cross-linked rubber Download PDFInfo
- Publication number
- CN1233703C CN1233703C CN 03150041 CN03150041A CN1233703C CN 1233703 C CN1233703 C CN 1233703C CN 03150041 CN03150041 CN 03150041 CN 03150041 A CN03150041 A CN 03150041A CN 1233703 C CN1233703 C CN 1233703C
- Authority
- CN
- China
- Prior art keywords
- rubber
- plastics
- tackifier
- oil
- thermoplastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 192
- 239000005060 rubber Substances 0.000 title claims abstract description 191
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 60
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229920003023 plastic Polymers 0.000 claims abstract description 72
- 239000004033 plastic Substances 0.000 claims abstract description 72
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 238000004073 vulcanization Methods 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 16
- 229920002367 Polyisobutene Polymers 0.000 claims abstract description 13
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 claims abstract description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 5
- 230000032683 aging Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 29
- 239000003921 oil Substances 0.000 claims description 28
- 239000004743 Polypropylene Substances 0.000 claims description 15
- -1 trans-isoprene Polymers 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 244000043261 Hevea brasiliensis Species 0.000 claims description 7
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 7
- 229920003052 natural elastomer Polymers 0.000 claims description 7
- 229920001194 natural rubber Polymers 0.000 claims description 7
- 229940099259 vaseline Drugs 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 229920013649 Paracril Polymers 0.000 claims description 3
- 239000005662 Paraffin oil Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920000800 acrylic rubber Polymers 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 claims description 3
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000010913 used oil Substances 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- MSAVICZWFPQFPO-UHFFFAOYSA-N acetic acid;ethene Chemical group C=C.C=C.CC(O)=O MSAVICZWFPQFPO-UHFFFAOYSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 20
- 238000012545 processing Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000004636 vulcanized rubber Substances 0.000 abstract 5
- 238000004873 anchoring Methods 0.000 abstract 4
- 239000004902 Softening Agent Substances 0.000 abstract 1
- 239000007859 condensation product Substances 0.000 abstract 1
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 27
- 230000001070 adhesive effect Effects 0.000 description 17
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 6
- 229920002943 EPDM rubber Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- JZQOYVNECBLUKM-UHFFFAOYSA-N C=O.NC(=O)N.C(CCCCCCC)C1=C(C=CC=C1)O Chemical class C=O.NC(=O)N.C(CCCCCCC)C1=C(C=CC=C1)O JZQOYVNECBLUKM-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 235000011150 stannous chloride Nutrition 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229920001617 Vinyon Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000010458 rotten stone Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
Abstract
The present invention relates to a method for preparing high-cohesiveness thermoplastic vulcanized rubber, particularly to a method for preparing thermoplastic vulcanized rubber by a dynamic full vulcanization technology. The present invention comprises the following operation steps: premixing rubber, plastics and an anchoring agent: partial rubber and all plastics are premixed with the anchoring agents, wherein the use level of the rubber which is premixed accounts for 20% to 60% of the total weight of rubber in the thermoplastic vulcanized rubber to be prepared, the use level of the anchoring agent accounts for 2% to 4% of the total weight of the thermoplastic vulcanized rubber to be prepared, and the anchoring agent is a condensation product of polyisobutylene or butylphenol and acetylene; [2] preparing rubber masterbatch: the rest rubber, filling material, softening agents, ageing agents and processing agents are mixed into masterbatch; [3] dynamically vulcanizing material: the mixing material prepared in the two steps, the rubber masterbatch, vulcanizing agents and accelerating agents are dynamically vulcanized; [4] charing oil in the later period: oil which comprises 20 wt. % of plastics is added to be continually and uniformly blended, and the thermoplastic vulcanized rubber with the advantages of high cohesiveness and good combination properties is obtained.
Description
Technical field the present invention relates to the method that a kind of dynamic full vulcanization technology prepares the high-adhesion thermoplastic sulfurized rubber, preparing the preparation method who proposes on the original prescription of the thermoplastic sulfurized rubber basis with melt-blending process, this method can prepare the thermoplastic sulfurized rubber of the high comprehensive performance of high-adhesion.
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 sulfurized rubber (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 the processing characteristics of thermoplastic material, replaces 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, 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/PPTPV) 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, the rubber adding is mixed together again, and then add auxiliary agent successively, filler and tenderizer mix, and add vulcanizing agent and promotor at last and carry out dynamic vulcanization.The preparation technology of blending type thermoplastic cross-linked rubber is at " Kinetic Model of Dynamic Vulcanization " (Polym.Mater.sci.Eng1998,79 102-103) 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.
The research in relevant this field mainly concentrated on raw material cooperation aspect both at home and abroad in recent years, as U.S. Advanced Elastomer Systems, L.P. [AES.Co.] " 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 from greater than 5.5 to the highest by about 20, prepared thermoplastic elastomer can also improve processing characteristics in the good physicals of maintenance." 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 method of tertiary blending has been proposed, two kinds of rubber constituents are arranged in this blend, combination as isobutene rubber and ethylene-propylene rubber(EPR) or natural rubber, tertiary blending helps improving the over-all properties of blend, and can improve the adhesive property of material to a certain extent." Thermoplastic elastomers based upon chlorinated polyethyleneand a crystalline olefin polymer " (U.S. Pat 4,978,716) poly-blended method has been proposed, this blend has two kinds of plastics, as chlorinatedpolyethylene and polypropylene, polynary plastics help to improve the degree of crystallinity and the flowability of plastics phase mutually, thereby prepare the TPV of excellent performance." Modification of thermolastic vulcanizates with athermoplastic random copolymer of ethylene " (U.S. Pat 6,399,710) proposed the employing random copolymers as plastics external phase, this invention thinks that random copolymers helps improving the tensile yield of material.Though can improve the adhesive property of TPV to a certain extent on above-mentioned starting material cooperate, from using producer's feedback information of TPV, the bond effect of this material is still not ideal enough.It is poor why thermoplastic sulfurized rubber and other elastomeric materials bond, and mainly is that well-known, the adhesive property of plastics and rubber is very poor because the external phase of thermoplastic sulfurized rubber is plastics.The contriver is from the result of the stripping strength of the commercially available external TPV material of lab investigation, and its adhesive property also is dissatisfactory.As the TPV of the Santoprene64A～80A of AES company, stripping strength only has 1.6～2.5KN/m (testing method adopts GB532-91 to test, and the T type is peeled off for 180 °, and draw speed is 100mm/min) on polarity formula rubber puller system.Summary of the invention the objective of the invention is to propose a kind of high-adhesion can the preparation method of thermoplastic sulfurized rubber.This method is to add tackifier in part rubber and plastics premix stage, allows tackifier homodisperse and participate in the dynamic vulcanization process in rubber and plastics two-phase, can make rubber phase all have reasonable adhesive property mutually with plastics like this.Studies have shown that tackifier can improve the adhesive property of TPV and other material greatly and do not reduce other performance of TPV in certain amount ranges.This method not only makes thermoplastic sulfurized rubber have good high-adhesion energy, and also has high workability, low compression deformation, soft simultaneously.
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 technical solution used in the present invention comprises following four steps:
1) rubber, plastics and tackifier premix: earlier part rubber and whole plastics and tackifier are mixed being higher than under the plastics fusing point, the rubber consumption that participates in premix accounts for 20%～60% of rubber gross weight in the thermoplastic sulfurized rubber that will prepare, the tackifier consumption is 2%～4% of the thermoplastic sulfurized rubber gross weight that will prepare, and tackifier are the condenses of polyisobutene or butylphenol and acetylene;
2) remaining rubber is prepared into rubber master batch: become rubber master batch with the remaining rubber of previous step and filler, tenderizer, aging agent, processing aid are mixing;
3) dynamic vulcanization: will go up the pre-composition of rubber, plastics and tackifier of two step preparations and rubber rubber master batch and vulcanizing agent, promotor and carry out dynamic vulcanization;
4) later stage is oil-filled: in the dynamic vulcanization later stage or after finishing, add 20% oil of plastics weight content, continue to mix.Promptly obtain the thermoplastic sulfurized rubber of high tackifying, high workability low compression deformation soft through above four steps.
The used rubber of the present invention is known thermoplastic sulfurized rubber rubber commonly used, for example: terpolymer EP rubber, isoprene-isobutylene rubber, trans-isoprene, natural rubber, 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: polyethylene, polypropylene, 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 and tackifier premix; The 2nd, oil-filled technology of later stage.
It is very even that rubber and plastic premix technology makes that rubber and the tackifier of plastics and part are pre-mixed, further add rubber after, whole rubber and plastics and tackifier 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 and tackifier 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, plastics and tackifier, for successfully realizing phase reversion in next step dynamic vulcanization process and obtaining the tiny particle that is evenly coated mutually by plastics is crucial, and tiny rubber particles also is indispensable for the flowability and the elasticity that improve TPV.
Oil-filled technology of later stage is meant to add in the dynamic vulcanization later stage again and accounts for 20% the oil that is equivalent to plastic content 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 present invention is except that for the existing known rubber and plastics commonly used, and 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.
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), only increase this component of tackifier, adopt homodisperse tackify technological method of the present invention, the thermoplastic sulfurized rubber of preparation high-adhesion energy.
Tackifier that the present invention adopts mainly contain two kinds, first polyisobutene, and for example with No. 2 polyisobutene of Xinjiang Xinfeng Co., Ltd.'s production, according to this product introduction, it mainly contains the purposes of following five aspects: 1) can be used for producing three big serial dispersion agents.2), be used for improving properties-correcting agent such as the adhesive property of thermoset rubber and fiber and rubber, paraffin, pitch as adhesion auxiliary material.3) be used as high-tension cable and protect the component of ointment, electric insulation resin, insulation pressure sensitive adhesives, insulation tape, industrial transformers wet goods.4) as joint filling crack and sealing material.5) be used for foodstuff additive.In rubber materials, polyisobutene can be used as tackifier, but mainly is the adhesive property that is used in framework materials such as improving thermoset rubber work in-process and fiber, and consumption generally is about 4% of a rubber consumption.In the thermoplastic sulfurized rubber field, the adhesive property that improves plastics and rubber base material by the way of adding tackifier is never arranged traditionally, improve the adhesive property aspect of thermoplastic sulfurized rubber and rubber with polyisobutene and never appear in the newspapers.It two is KORESIN resins of German BASF, is the condenses of butylphenol and acetylene, is used as the tackifier that improve the tire cohesive force in the rubber industry, and amount ranges generally is 2～5%.
The present invention introduces tackifier by the rubber and plastic premix stage at the external phase plastics cleverly by the way of adding tackifier, thereby improves the adhesive property of thermoplastic sulfurized rubber, and this method yet there are no report in the thermoplastic sulfurized rubber field.Why the present invention adds tackifier in the rubber and plastic premix stage mainly is to consider that adding tackifier in the rubber and plastic premix stage can make tackifier relatively be dispersed in rubber and plastics two Xiangli, make tackifier can bring into play good effect, allow disperse phase rubber and external phase plastics that reasonable adhesive property is all arranged.The stripping strength of the thermoplastic sulfurized rubber that makes with the inventive method can reach 5.2KN/m, and this is the highest level of present thermoplastic sulfurized rubber, is better than the adhesive property (generally being lower than 2.5KN/m) of commercially available TPV material greatly.Add tackifier if adopt in traditional rubber master batch method, tackifier can only be treated in rubber phase so, and can not make plastics that reasonable adhesive property is arranged; If add tackifier in the dynamic vulcanization process, will influence the dynamic vulcanization process so, make that other performances of prepared material are not ideal enough.Adopt the performance and comparing of the prepared thermoplastic sulfurized rubber of the present invention by the conventional art preparation, the thermoplastic sulfurized rubber of the technology of the present invention preparation is being higher than the prepared cross-linked rubber of traditional technological method far away aspect the adhesive property (showing the stripping strength of material), the stripping strength of commercially available TPV material generally is not higher than 2.5KN/m, (as: can hang down to 26% by compression set in other performances for the TPV for preparing by present technique, hardness can be hanged down to 60 shore As, tensile strength can reach tens Mpa) stripping strength can reach 5.2KN/m under the prerequisite that is maintained substantially, and adhesive property has improved nearly twice.
Embodiment
The performance of the thermoplastic sulfurized rubber of the embodiment of the invention and Comparative Examples preparation is listed in the table 1.
Embodiment 1 preparation rubber and plastic is than EPT rubber (EPDM/PP) the blending type thermoplastic cross-linked rubber that is 60/40, the tackifier polyisobutene that participates in premix account for prepared thermoplastic sulfurized rubber prescription gross weight 2%), No. 2 polyisobutene that tackifier are produced with Xinjiang Xinfeng Co., Ltd..
Operation steps is as follows:
1) antioxidant 1010 and the 8.1 gram polyisobutene tackifier with 24 gram terpolymer EP rubbers, 80 gram acrylic plastering, 0.8 gram mix in 170 ℃ twin-roll plasticator, and are 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 1.2 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 EPDM/PP blending type thermoplastic cross-linked rubber that is 60/40.Performance sees Table 1
Embodiment 2 preparation rubber and plastics are than isoprene-isobutylene rubber/polypropylene (IIR/PP) blending type thermoplastic cross-linked rubber that is 70/30, the tackifier KORESIN resin that participates in premix accounts for 3% of prepared thermoplastic sulfurized rubber prescription gross weight, and tackifier are the butylphenol of German BASF and the condenses KORESIN resin of acetylene.
1) antioxidant 1010 and the 12.8 gram KORESIN tackifier resins with 56 gram isoprene-isobutylene rubbers, 60 gram acrylic plastering, 0.6 gram mix in 170 ℃ mixing tank, and are about 3 minutes, standby;
The 84 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 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 12 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 70/30.Performance sees Table 1.From the performance table as seen, even dissimilar thermoplastic vulcanizates and dissimilar tackifier so long as the cross-linked rubber by the technology of the present invention preparation, just can reach the purpose of high-adhesion.
Embodiment 3 preparation rubber and plastics than be natural rubber/polyethylene (NR/PE) blending type thermoplastic cross-linked rubber of 50/50 (participate in the tackifier tackifier polyisobutene of premix, account for prepared thermoplastic sulfurized rubber fill a prescription gross weight 4%)
1) antioxidant 1010 and the 14.8 gram polyisobutene tackifier with 60 gram natural rubbers, 100 gram vinyons, 1.0 grams mix in 170 ℃ mixing tank, and are about 3 minutes, standby;
The 40 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 1.0 grams successively on a small quantity, the white carbon black of 40 grams is played 6 triangle bags, adds 100 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 10.0 gram uncle octyl phenol urea formaldehydes, mixes 30 seconds, adds 2.0 gram tin protochlorides at last and carries out dynamic vulcanization 15 minutes;
4) add 20 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 50/50.Performance sees Table 1.From the performance table as seen, even different rubber and plastic than, dissimilar thermoplastic sulfurized rubber, so long as the cross-linked rubber by the technology of the present invention preparation, just can reach the purpose of high-adhesion.
Comparative Examples 1 conventional dynamic sulfurization technology prepares rubber and plastic than EPT rubber (EPDM/PP) the blending type thermoplastic cross-linked rubber (composition of prescription and consumption are with example 1) that is 60/40
1) plastics and the antioxidant 1010 with whole consumptions drops into 170 ℃ twin-roll plasticator, until plasticizing evenly, and about 2 minutes.
2) again the terpolymer EP rubber of whole consumptions is dropped in the plastics that the first step plastifies, be mixed to evenly after, add 8.1 gram polyisobutene tackifier.
3) after the rubber and plastic of previous step and tackifier mix, repeatedly add white carbon black successively on a small quantity and and with oil in batches.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.Compare as seen with embodiment 1 from table 1, same recipe is with the cross-linked rubber of conventional art preparation
The cross-linked rubber that on adhesive property, prepares not as the technology of the present invention.Comparative Examples 2 preparation rubber and plastics are than isoprene-isobutylene rubber/polypropylene (IIR/PP) blending type thermoplastic cross-linked rubber that is 70/30.As seen (method is identical with embodiment 2, and difference is without tackifier in prescription) compare with embodiment 2 from table 1, and the adding of tackifier can improve the tackifying of material greatly.
Table 1
| Hardness (Shao A) | 100% stretches (MPa) surely | Tensile strength (MPa) | Elongation (%) | Tear strength (KN/m) | Tensile set (%) | 100 ℃ * 22h of compression set (%) | Stripping strength KN/m | |
| Embodiment 1 | 68 | 3.0 | 12.1 | 420 | 34.6 | 20 | 30 | 4.9 |
| Embodiment 2 | 60 | 2.4 | 9.6 | 380 | 30.0 | 16 | 26 | 5.1 |
| Embodiment 3 | 80 | 5.1 | 16.1 | 430 | 48.0 | 16 | 38 | 5.2 |
| Comparative Examples 1 | 73 | 3.6 | 12.4 | 410 | 34.8 | 20 | 40 | 1.3 |
| Comparative Examples 2 | 60 | 2.3 | 9.5 | 380 | 30.0 | 16 | 26 | 1.3 |
Claims (4)
1. the preparation method of a high-adhesion 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 and tackifier premix: earlier with part rubber with all plastics and tackifier mix being higher than under the plastics fusing point, the rubber consumption that participates in premix accounts for the 20%-60% of rubber gross weight in the thermoplastic sulfurized rubber that will prepare, the tackifier consumption is thermoplastic sulfurized rubber gross weight 2%-4%, and tackifier are the condenses of polyisobutene or butylphenol and acetylene;
(2) preparation of rubber rubber master batch: become rubber master batch with the remaining rubber of previous step and filler, tenderizer, aging agent, processing aid are mixing;
(3) dynamic vulcanization: will go up the pre-composition of rubber, plastics and tackifier of two step preparations and rubber rubber master batch and vulcanizing agent, promotor and carry out dynamic vulcanization;
(4) later stage is oil-filled: in the dynamic vulcanization later stage or after finishing, add 20% oil of plastics weight content, continue to mix, promptly obtain commixed type high-adhesion thermoplastic sulfurized rubber.
2. the preparation method of thermoplastic sulfurized rubber according to claim 1, it is characterized in that: rubber is terpolymer EP rubber, isoprene-isobutylene rubber, natural rubber, trans-isoprene, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), ethene-acetate ethylene 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 polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene terpolymer, vinylbenzene-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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150041 CN1233703C (en) | 2003-07-31 | 2003-07-31 | Method for preparing high-cohesiveness thermoplastic cross-linked rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150041 CN1233703C (en) | 2003-07-31 | 2003-07-31 | Method for preparing high-cohesiveness thermoplastic cross-linked rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1580098A CN1580098A (en) | 2005-02-16 |
| CN1233703C true CN1233703C (en) | 2005-12-28 |
Family
ID=34579773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03150041 Expired - Lifetime CN1233703C (en) | 2003-07-31 | 2003-07-31 | Method for preparing high-cohesiveness thermoplastic cross-linked rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1233703C (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101597378B (en) * | 2008-06-04 | 2011-11-09 | 四川晨光科新塑胶有限责任公司 | Method for preparing thermoplastic dynamic perduren |
| CN101696279B (en) * | 2009-10-22 | 2012-01-11 | 金发科技股份有限公司 | Method for preparing thermoplastic elastomer through dynamic vulcanization |
| CN101817957B (en) * | 2010-04-09 | 2012-07-04 | 北京化工大学 | Low-lag microcellular rubber material for oscillation reduction of high-speed railway fastener and preparation method thereof |
| CN102443218B (en) * | 2011-09-23 | 2013-12-25 | 郑勇 | Thermoplastic rubber composition and preparation method thereof |
| CN103819773A (en) * | 2014-02-28 | 2014-05-28 | 苏州瑞邦塑胶有限公司 | Improved TPV formula |
| CN106700976A (en) * | 2016-11-09 | 2017-05-24 | 安徽中翰高分子科技有限公司 | Thermoplastic vulcanized rubber material serving as bonding base material |
| CN107383835B (en) * | 2017-08-31 | 2019-04-05 | 彭超昀莉 | A kind of step up cure automobile spoiler and preparation method thereof |
| CN107337916B (en) * | 2017-08-31 | 2019-04-05 | 彭超昀莉 | Cold-resistant automobile spoiler and preparation method thereof |
| CN109749181A (en) * | 2017-11-01 | 2019-05-14 | 丹阳博亚新材料技术服务有限公司 | A kind of pressure resistance insulating materials |
| CN110872477A (en) * | 2018-09-03 | 2020-03-10 | 中国石油天然气集团有限公司 | Butyl pressure-sensitive adhesive and preparation method and application thereof |
| CN109294246A (en) * | 2018-09-21 | 2019-02-01 | 南京京锦元科技实业有限公司 | Phenolic curing TPV material of a kind of soft height rebound and preparation method thereof |
| CN109721857A (en) * | 2018-11-23 | 2019-05-07 | 东莞捷佳塑胶科技有限公司 | Improve the new auxiliary formula of TPV |
| 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 |
| CN114381047B (en) * | 2022-01-26 | 2023-07-04 | 宁波磐固工程技术有限公司 | Memory rubber with high cohesiveness and preparation method and application thereof |
-
2003
- 2003-07-31 CN CN 03150041 patent/CN1233703C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1580098A (en) | 2005-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1233703C (en) | Method for preparing high-cohesiveness thermoplastic cross-linked rubber | |
| CN100400574C (en) | Method for raising fluidity of thermoplastic cross-linked rubber | |
| CN102051000B (en) | TPV (Thermoplastic Vulcanizate) elastomeric material with improved electrical property | |
| CN107227027B (en) | Thermoplastic composite elastomer and preparation method and application thereof | |
| CN103044696A (en) | Preparation method of thermoplastic vulcanized rubber | |
| US6262175B1 (en) | Thermoplastic elastomer composition | |
| CN110452467A (en) | A kind of thermoplastic elastomer (TPE) and preparation method thereof with inierpeneirating network structure | |
| CN101845193A (en) | Dynamically vulcanized styrene thermoplastic elastomer and preparation method thereof | |
| CN111849069A (en) | Composite rubber thermoplastic elastomer and preparation method thereof | |
| CN1227285C (en) | Method for preparing thermoplastic cross-linked rubber | |
| CN1218990C (en) | Preparation method of starch and polymer comosition | |
| CN114058097B (en) | High-performance uncrosslinked rubber asphalt and preparation method thereof | |
| CN103102578A (en) | Low temperature-resistant thermoplastic elastomer and preparation method thereof | |
| CN1304476C (en) | Method for preparing tribasic ethylene propylene rubber/polypropylene thermoplastic elastomer | |
| CN1302065C (en) | New type polyolefin thermoplastic elastomer | |
| CN1063199C (en) | High-toughness polypropylene composite | |
| CN111138754A (en) | High-fluidity and high-rigidity alloy composite material and preparation method thereof | |
| CN112759816B (en) | Composition for preparing halogen-free flame-retardant ethylene octene copolymer/polylactic acid thermoplastic elastomer, and preparation method and application thereof | |
| Ichazo et al. | Comparison of rheological and mechanical behavior of dynamically and statically vulcanized PP/SBS blends | |
| CN87102663A (en) | Plastic filler parent granule | |
| CN111320796A (en) | Preparation method and application of multi-component composite modifier | |
| CN1188469C (en) | Toughening polyamide combination and prepn method | |
| CN104629191A (en) | Rubber plastic blended composition, dynamically vulcanized thermoplastic elastomer and preparation method thereof | |
| CN113831650B (en) | Heat-resistant and wear-resistant TPV composition and preparation method thereof | |
| CN112625437B (en) | Nylon 66 thermoplastic elastomer material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20081128 Address after: East head of Longkou Economic Development Zone, Shandong, Longkou City Patentee after: Shandong dawn north of elastomer material Co.,Ltd. Address before: Beijing City, Chaoyang District North Ring Road No. 15 Patentee before: Beijing University of Chemical Technology |
|
| ASS | Succession or assignment of patent right |
Owner name: SHANDONG DOWN BEIHUA ELASTOMER MATERIALS CO., LTD. Free format text: FORMER OWNER: BEIJING CHEMICAL ENGINEERING UNIV. Effective date: 20081128 |
|
| ASS | Succession or assignment of patent right |
Owner name: LONGKOU DAWN ENGINEERING PLASTIC CO., LTD. Free format text: FORMER OWNER: SHANDONG DAWN BEIHUA ELASTOMER MATERIAL Effective date: 20100906 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 265703 EAST END OF LONGKOU ECONOMIC DEVELOPMENT ZONE, LONGKOU CITY, SHANDONG PROVINCE TO: 265701 INDUSTRIAL ZONE, DAOEN ECONOMIC PARK, NORTH END OF ZHENXING ROAD, LONGKOU CITY, SHANDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20100906 Address after: 265701 Shandong Province, Longkou City revitalization of the first northbound dawn Economic Industrial Park Patentee after: LONGKOU DAWN ENGINEERING PLASTIC Co.,Ltd. Address before: 265703 East head of Longkou Economic Development Zone, Shandong, Longkou City Patentee before: Shandong dawn north of elastomer material Co.,Ltd. |
|
| C56 | Change in the name or address of the patentee |
Owner name: SHANDONG DAWN POLYMER CO., LTD. Free format text: FORMER NAME: LONGKOU DAWN ENGINEERING PLASTIC CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 265701 Shandong Province, Longkou City revitalization of the first northbound dawn Economic Industrial Park Patentee after: SHANDONG DAWN POLYMER Co.,Ltd. Address before: 265701 Shandong Province, Longkou City revitalization of the first northbound dawn Economic Industrial Park Patentee before: LONGKOU DAWN ENGINEERING PLASTIC Co.,Ltd. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20051228 |
|
| CX01 | Expiry of patent term |