KR980009354A - Process for preparing organosilane polysulfane mixtures and rubber blends containing such mixtures - Google Patents
Process for preparing organosilane polysulfane mixtures and rubber blends containing such mixtures Download PDFInfo
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- KR980009354A KR980009354A KR1019970033564A KR19970033564A KR980009354A KR 980009354 A KR980009354 A KR 980009354A KR 1019970033564 A KR1019970033564 A KR 1019970033564A KR 19970033564 A KR19970033564 A KR 19970033564A KR 980009354 A KR980009354 A KR 980009354A
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- rubber
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- organosilanepolysulfane
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- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 229920001971 elastomer Polymers 0.000 title claims abstract description 27
- 239000005060 rubber Substances 0.000 title claims abstract description 27
- 150000001282 organosilanes Chemical class 0.000 title claims abstract description 11
- 229910000057 polysulfane Inorganic materials 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000009472 formulation Methods 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- 239000000945 filler Substances 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 11
- 238000005096 rolling process Methods 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920003052 natural elastomer Polymers 0.000 claims description 6
- 229920001194 natural rubber Polymers 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- 229920003051 synthetic elastomer Polymers 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000005061 synthetic rubber Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 239000004927 clay Substances 0.000 claims 1
- 150000004760 silicates Chemical class 0.000 claims 1
- 238000013329 compounding Methods 0.000 abstract description 10
- 238000009991 scouring Methods 0.000 abstract description 6
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract 1
- 235000019241 carbon black Nutrition 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- 238000010058 rubber compounding Methods 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IKRMQEUTISXXQP-UHFFFAOYSA-N tetrasulfane Chemical group SSSS IKRMQEUTISXXQP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- -1 (triethoxysilylpropyl)- Chemical class 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- XWSQTXBRVIEOGT-UHFFFAOYSA-N triethoxy-[3-(tetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSS XWSQTXBRVIEOGT-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
본 발명은 화학식 1의 오가노실란폴리설판 혼합물과 이러한 혼합물을 사용하여 제조된 고무 배합물에 관한 것이고, 특히 타이어 트레드에 관한 것이다.The present invention relates to organosilanepolysulfane mixtures of formula (1) and rubber blends prepared using such mixtures, in particular to tire treads.
(1) (One)
위의 화학식 1에서, R은 탄소수 1 내지 8, 특히 탄소수 1 내지 3의 선형 또는 측쇄 알킬이고, x는 1 내지 8의 정수이며, z는 0 내지 6이다(여기서 z=0인 오가노실란폴리설판 비율과 z=1인 오가노실란폴리설판 비율의 합은 80중량% 이상이고, 단 z=0인 화합물의 비율은 80% 미만이고, z가 2 내지 6의 정수인 오가노실란폴리설판의 비율은 혼합물 중에서 20중량% 비율을 초과하지 않는다.)In the above formula (1), R is linear or branched alkyl of 1 to 8 carbon atoms, in particular 1 to 3 carbon atoms, x is an integer of 1 to 8, z is 0 to 6 (where z = 0 organosilane poly The sum of the sulfonate ratio and the ratio of organosilanepolysulfane with z = 1 is 80% by weight or more, provided that the ratio of the compound with z = 0 is less than 80% and the ratio of organosilanepolysulfane with z being an integer of 2 to 6 Does not exceed 20% by weight of silver in the mixture.)
[도면의 간단한 설명][Brief Description of Drawings]
제1도는 실시예 1에 따른 배합물의 최소 토오크 값을 도시.1 shows the minimum torque values of the formulations according to Example 1. FIG.
제2도는 Si 266 모드 Si 69의 모든 배합 온도에서의 스코칭 거동을 도시,2 shows the scouring behavior at all compounding temperatures of Si 266 mode Si 69,
제3도는 Si 266 모드 Si 69의 모든 배합 온도에서의 경화 시간을 도시,3 shows the curing time at all blending temperatures of Si 266 mode Si 69,
제4도는 Si 266 모드 Si 69의 모든 배합 온도에서의 가공 거동을 도시,4 shows the processing behavior at all compounding temperatures of Si 266 mode Si 69,
제5도는 Si 266 모드 Si 69의 모든 배합 온도에서의 주입 속도를 도시,5 shows the injection rates at all compounding temperatures of Si 266 mode Si 69,
Description
본 발명은 디설판 비율이 상승된 오가노실란폴리설판 혼합물과 이러한 배합물을 함유하고 고무 배합물의 제조방법에 관한 것이다.The present invention relates to organosilanepolysulfane mixtures having elevated disulfane ratios and to methods for preparing rubber blends containing such blends.
환경에 대한 자각이 증가하여, 연료 소비량 절약과 오염물질 배출 감소가 최근 점점 우선시되어 가고 있다[문헌 참고: Auto 91/92, Verband der Artomobilindustrie e.V., Frankfurt 및 ADAC-Motorwelt 11791, 50(1991)]. 타이어 제조자들이 목표는 탁월한 습윤 미끄럼 저항과 우수한 마멸 저항과 함께 매우 낮은 구름 저항을 나타내는 타이어를 개발하는 것이다.With increased awareness of the environment, savings in fuel consumption and reduction of pollutant emissions have become increasingly important in recent years (see Auto 91/92, Verband der Artomobilindustrie e.V., Frankfurt and ADAC-Motorwelt 11791, 50 (1991)). The goal of tire manufacturers is to develop tires that exhibit very low rolling resistance with excellent wetting slip resistance and good abrasion resistance.
여러 문헌과 특허에 타이어 구름 저항을 감소시켜 연료 소비량을 감소시키는 것에 대한 것이 제안되어 있다. 언급된 제안에는 배합물 속의 카본 블랙 함량을 감소시키고 특수한 카본 블랙을 사용하는 것이 있다(문헌 참조 : 미국 특허 제4,866,131호 및 미국 특허 제4,894,420호). 그러나, 이처럼 제안된 해결책 중에서 어떤 것도 습윤 미끄럼 저항과 마멸 저항과 같은 기타 중요한 타이어 특징과 목적하는 낮은 구름 저항 사이의 균형을 만족시키지 못하고 있다. 고무 배합물 속의 카본 블랙을 실리카로 다량 치환한 경우, 오가노실란 비스(트리에톡시실릴프로필)테트라설판과 배합하여 고활성 실키카 충전제를 사용할 때만 표준 타이어와 비교하여, 거의 감소된 구름 저항을 갖는 동시에 위에서 기술한 다른 2가지의 타이어 특징을 유지하거나 더욱 향상시키면서, 타이어 제조가 진척되었다.(문헌 참조 : 유럽 특히 제0,501,227호, 미국 특허 제5,227,425호; G. Agostini, J. Berg, Th. Materne: New Compound Technology, October 1994, Akron, Ohio, USA; S. Wolff, U. Gorl, M.J. Wang, W. Wolff: Silica based on tread compounds-background & perfomance, paper presented at TYRE TECH '93, October 1993, Basel, Swizerland 및 Ph. Cochet, L.B. Barriquand: Precipitated silica in tire tread, paper presented at ACS Meeting of the Rubber Division, October 1995, Cleveland, Ohio, USA).Several documents and patents propose reducing fuel consumption by reducing tire rolling resistance. The mentioned proposals include reducing the carbon black content in the formulation and using special carbon blacks (see US Pat. No. 4,866,131 and US Pat. No. 4,894,420). However, none of these proposed solutions satisfies the balance between other important tire features such as wet skid and abrasion resistance and the desired low rolling resistance. When carbon black in the rubber compound is largely substituted with silica, it has almost reduced rolling resistance compared to standard tires only when high active silica gel filler is used in combination with organosilane bis (triethoxysilylpropyl) tetrasulfane. At the same time, tire manufacturing has been advanced while maintaining or further improving the other two tire features described above. (See, e.g., European Patent No. 0,501,227, US Patent No. 5,227,425; G. Agostini, J. Berg, Th. Materne New Compound Technology, October 1994, Akron, Ohio, USA; S. Wolff, U. Gorl, MJ Wang, W. Wolff: Silica based on tread compounds-background & perfomance, paper presented at TYRE TECH '93, October 1993, Basel, Swizerland and Ph. Cochet, LB Barriquand: Precipitated silica in tire tread, paper presented at ACS Meeting of the Rubber Division, October 1995, Cleveland, Ohio, USA).
뉴욕에서의 1986년 ACS 학회에서 에스. 볼프(문헌 참조: S. Wolff: The influence of fillers on rolling resistance, presented at the 129th meeting of the Rubber Division, American Chemical Society, April 811, 1986, New York)는 유화제 스티렌/부타디엔 고무(E-SBR)로 기제화한 승용차 타이어 트레드와 천연고무로 기제화한 화물차 타이어 트레드 둘 다에 TESPT로 배합하여 실리카를 사용하여 습윤 미끄럼 저항을 상당히 유지시키면서 카본 블랙으로 충전된 표준 배합물과 비교할 때 구름 저항을 뚜렷하게 감소시킬 수 있다고 보고하였다.S at the 1986 ACS conference in New York. Wolff (S. Wolff: The influence of fillers on rolling resistance, presented at the 129th meeting of the Rubber Division, American Chemical Society, April 811, 1986, New York) is emulsifier styrene / butadiene rubber (E-SBR) TESPT is incorporated into both passenger car treads based on carbon steel and truck tire treads based on natural rubber to significantly reduce the rolling resistance when compared to standard formulations filled with carbon black, while maintaining significant wet sliding resistance using silica. Reported.
추가로 이러한 시스템은, 때로는 기타 중합제(특히 부타디엔)와 블렌딩하여, 용액 중합 공정(문헌 참조: 유럽 특허 제0 447 066 A1호)을 사용하여 제조한 특수한 스티렌/부타디엔 중합체 및 신규한 실리카 등급(문헌 참조: 미국 특허 제5,227,425호)과, 때로는 3 내지 4개의 상이한 출발 중합체를 갖는 이 출원(유럽 특허 제0 620 250 A1)에 특별히 적합한 중합체 블렌드를 사용함으로써 3가지 특징을 모두 최적화시킨다(문헌 참조: G.W. Marwede, U.G. Eisele, A.J.M Sumner: paper presented to the ACS Meeting of the Rubber Division, October 1995, Cleveland, Ohio, USA 및 U. LeMaitre: Tire Rolling resistance, AFCEP/DKG Meeting, 1993, Mulhouse, France).In addition, these systems are often blended with other polymerizers (especially butadiene) to produce special styrene / butadiene polymers and novel silica grades prepared using a solution polymerization process (see EP 0 447 066 A1). Literature reference: All three features are optimized by using polymer blends that are particularly suitable for this application (European Patent No. 0 620 250 A1) and sometimes with 3 to 4 different starting polymers (see Literature 5). GW Marwede, UG Eisele, AJM Sumner: paper presented to the ACS Meeting of the Rubber Division, October 1995, Cleveland, Ohio, USA and U. LeMaitre: Tire Rolling resistance, AFCEP / DKG Meeting, 1993, Mulhouse, France).
모든 문헌과 특허에는, 습윤 미끄럼 저항과 마멸 저항을 유지하거나 향상시키면서 더 낮은 구름 저항을 성취하기 위해서 통상 사용되는 카본 블랙 충전제의 높은 비율 또는 전체 합량을 고활성 실리카로 치환시킬 필요가 있다고 기술되어 있다(문헌 참조: S. wolff: The influence of fillers on rolling resistance, presented at the 129th meeting of the Rubber Division, American Chemical Society, April 811, 1986, New York 및 U. LeMaire: Tire rolling resistance, AFCEP/DKG Meeting, 1993, Mulhouse, France). 그러나, 이러한 치환은 오가노실란비스(트리에톡시실릴프로필)테트라설판(TESTP)을 실리카와 중합체간의 “커플링제”로서 사용하는 경우에만 목적을 성취할 수 있다.All documents and patents state that it is necessary to replace high proportions or total amounts of carbon black fillers commonly used with highly active silica to achieve lower rolling resistance while maintaining or improving wet slip and wear resistance. (See S. wolff: The influence of fillers on rolling resistance, presented at the 129th meeting of the Rubber Division, American Chemical Society, April 811, 1986, New York and U. LeMaire: Tire rolling resistance, AFCEP / DKG Meeting , 1993, Mulhouse, France). However, this substitution can only achieve the purpose when organosilanebis (triethoxysilylpropyl) tetrasulfane (TESTP) is used as a "coupling agent" between silica and polymer.
고무 배합물에 오가노실란을 사용함으로써 성취되는 특성은 2개의 독립적인 반응에 좌우된다.(문헌 참조: S. Wolff: The role of rubber-to-silica bonds in reinforcement, presented at the First Franco-German Rubber Symposium, November 14-16, 1985, Obernai, France 및 S. Wolff: Silanes in tire compounding after ten years-review, Third Annual Meeting & Conference on Tire Science & Technology, The Tire Society, March 28-29, 1984, Akron, Ohio, USA). 먼저, 배합물 제조 동안, 바람직하게는 첫 번째 배합단계 동안, 승온에서 실리카의 실란을 그룹과 알콜을 제거한 실란의 트리알콕시실릴 그룹을 반응시킨다(소수성 반응 또는 개질 반응). 종결 반응은 후속 특성에 결정적으로 중요하다. 모든 화학반응에서와 같이, 이러한 반응은 승온에서 더 신속하게 진행되고, 짧은 배합시간을 요구하는 고무 배합기는 가능한 한 가장 높은 배합온도에 적합하다. 그러나 이처럼 높은 배합온도는, 두 번째의 이른바 TESPT의 고무 반응성 그룹이 더 장쇄의 설판(S5-S8)이 상당한 비유을 갖는 테트라설판 그룹을 평균으로 하는 그룹으로 이루어진 사실에 제한받는다(문헌 참조: S. Wolff: Silanes in tire compounding after ten years-review, Third Annual Meeting & Conference on Tire Science & Technology, The Tire Society, March 28-29, 1984, Akron, Ohio, USA).The properties achieved by using organosilanes in rubber formulations depend on two independent reactions (see S. Wolff: The role of rubber-to-silica bonds in reinforcement, presented at the First Franco-German Rubber). Symposium, November 14-16, 1985, Obernai, France and S. Wolff: Silanes in tire compounding after ten years-review, Third Annual Meeting & Conference on Tire Science & Technology, The Tire Society, March 28-29, 1984, Akron , Ohio, USA). First, during the preparation of the formulation, preferably during the first compounding step, the silane of silica is reacted with the trialkoxysilyl group of the silane having the alcohol removed at an elevated temperature (hydrophobic or reforming reaction). Termination reactions are critically important for subsequent properties. As with all chemical reactions, this reaction proceeds more rapidly at elevated temperatures, and rubber compounders requiring short compounding times are suitable for the highest possible blending temperatures. However, this high compounding temperature is limited by the fact that the second so-called rubber-reactive group of TESPT consists of a group in which the longer chains (S 5 -S 8 ) average the tetrasulfane group, which has a significant analogy (see literature). S. Wolff: Silanes in tire compounding after ten years-review, Third Annual Meeting & Conference on Tire Science & Technology, The Tire Society, March 28-29, 1984, Akron, Ohio, USA).
이러한 고무 반응성 그룹은 일반적으로 이른바 충전제/고무 결합으로 나타나는 것으로 여겨지며, 완제품(예를 들어, 타이어)에 대한 기술상의 고무 특성을 결정한다. 가황 동안 요구되는 이러한 반응은 테트라설판 그룹의 열 유연성과 더 높은 설판 단위에 영향을 받는다. 그러나 실제 실행에서, 반응이 가황되지 않은 배합물 제조 동안 일어나는 경우, 다만 충전제와 실란이 규칙적으로 반응하는 동안 일어나는 경우, 반응은 심각한 문제를 야기한다.Such rubber reactive groups are generally believed to appear as so-called filler / rubber bonds and determine the technical rubber properties for the finished product (eg tire). This reaction, which is required during vulcanization, is affected by the thermal flexibility of the tetrasulfane group and the higher sulfane units. In practical practice, however, if the reaction occurs during the preparation of the unvulcanized formulation, but only during the regular reaction of the filler and silane, the reaction causes serious problems.
황이 장쇄 설판 단위에서 제거되는 경우, 중합체 쇄에 혼입된다. 이는 “스코칭”을 초래하게 되고 시트댄 배합물을 경화시켜, 가황되지 않은 배합물을 더 이상 반응이 진행되지 않게 하기도 한다. 스코칭은 배합물의 점도를 결정함으로써 측정한다. 먼저 공보되지 않은 유럽 특허 제A1-0 732 362호에 고무 배합물에 오가노실란디설파이드를 사용하는 것이 기술되어 있다. 그러나, 이러한 황 배합물은 매우 순도가 높아야 하거나 디설파이드 함량이 80% 이상이어야 한다.When sulfur is removed in the long chain tongue plate unit, it is incorporated into the polymer chain. This results in "scoring" and also hardens the sheet dan blend, which may cause the unvulcanized blend to no longer react. Scorching is measured by determining the viscosity of the formulation. European Patent A1-0 732 362, which is not published first, describes the use of organosilanedisulfide in rubber formulations. However, these sulfur blends must be very pure or have a disulfide content of at least 80%.
본 발명의 목적은, 가황되지 않은 고무 배합물, 즉 가황에 필요한 황 또는 촉진제를 아직 함유하지 않는 가황성 고무 배합물의 제조 동안 발생할 수 있는 승온에서의 스코칭이 발생되지 않는 오가노실란폴리설판 혼합물을 제공하는 것이다.It is an object of the present invention to provide organosilanepolysulfane mixtures which do not result in scouring at elevated temperatures which may occur during the preparation of vulcanized rubber formulations, ie vulcanizable rubber formulations which do not yet contain sulfur or accelerators required for vulcanization. To provide.
본 발명은 이러한 목적을 성취하기 위해서 폴리설판 혼합물을 제공한다 이는 화학식 1의 오가노 실란폴리설판 혼합물을 포함한다.The present invention provides a polysulfane mixture to achieve this object, which includes an organo silanepolysulfane mixture of formula (1).
위의 화학식 1에서, R은 탄소수 1 내지 8, 특히 탄소수 1 내지 3의 선형 또는 측쇄 알칼이고, x는 1 내지 8의 정수이며, z는 0 내지 6이다(여기서, z=0인 오가노실란폴리설판 비율과 z=1인 오가노실란폴리설판 비율의 합은 80중량% 이상이고, 단 z=0인 화합물의 비율은 80%미만이고 z가 2 내지 6의 정수인 오가노실란폴리설판의 비율은 혼합물 중에서 20중량% 비율을 초과하지 않는다).In the above formula (1), R is a linear or branched chain alkali having 1 to 8 carbon atoms, in particular 1 to 3 carbon atoms, x is an integer of 1 to 8, z is 0 to 6 (where z = 0 organosilane The sum of the ratio of polysulfane and the ratio of organosilanepolysulfane with z = 1 is 80% by weight or more, provided that the ratio of the compound with z = 0 is less than 80% and the ratio of organosilanepolysulfane with z being an integer of 2 to 6 Does not exceed 20% by weight of silver in the mixture).
20중량% 비율을 초과하지 않는다는 것은 20중량% 이하로 언급되고 필수적으로 특징지어지는 특색이다. z=7 또는 z=8인 폴리설판 분획은 일반적으로 본 발명에 따르는 혼합물 중에서 발견되지 않는다. 예외적으로 이들은 본 발명에 따르는 혼합물의 사용에 어떠한 영향도 미치지 않는 1% 미만의 함량으로, 예를 들어 불순물로서, 존재한다.Do not exceed 20% by weight ratio is a feature that is referred to as 20% by weight or less and is characterized by nature. Polysulfane fractions with z = 7 or z = 8 are generally not found in the mixtures according to the invention. Exceptionally they are present in amounts of less than 1%, for example as impurities, which do not affect any use of the mixtures according to the invention.
물론 성분의 합은 경우에 따라, z=7 : 8인 배합물에 주의하여 항상 100%이어야 한다.Of course, the sum of the components should always be 100%, with care in the formulation with z = 7: 8, as the case may be.
오가노실란폴리설판 비율이 다음 값을 갖는 혼합물이 특히 적합한 혼합물이다.Mixtures in which the organosilanepolysulfane ratio has the following values are particularly suitable mixtures.
z=0 약 58% 내지 80% 미만 z=1 0초과 내지 약 32%(여기서, 이러한 배합물의 합은 80% 이상이다) z=2 내지 6 20% 이하, 특히 약 11% 미만.z = 0 greater than about 58% to less than 80% z = 1 greater than about 32%, where the sum of these combinations is greater than or equal to 80% z = 2 to less than or equal to 20%, in particular less than about 11%.
본 발명에 따라, 혼합물을 가황성 고무 배합물, 특히 타이어 제조에 사용한다. 이러한 배합물에 사용되는 중합체는 오일 중량되든지 되지 않는지, 중합체 단독으로서의 천연 엘라스토머 및 합성 엘라스토머 또는 용액 중합 공정 또는 유화중합 공정을 사용하여 제조한 예를 들어 천연 고무, 부타디엔 고무, 이소프렌 고무, 부타디엔/스티렌 고무, 특히 SBR과 같은 기타 고무와 블렌딩한 천연 엘라스토머 및 합성 엘라스토머이다. 한편 용어 혼합물은 화학식 1(여기서, x가 0이 아닌 경우, 청구항 1에서 정의하는 바와 같은, x=0인 다른 폴리설판이다)의 순수한 폴리설판으로부터 배합물을 제조할 수 있는 것을 의미한다.According to the invention, the mixtures are used for the production of vulcanizable rubber blends, in particular tires. The polymers used in such formulations may or may not be oil weighted, for example natural rubbers, butadiene rubbers, isoprene rubbers, butadiene / styrene rubbers prepared using natural and synthetic elastomers or solution polymerization processes or emulsion polymerization processes as polymers alone. Natural elastomers and synthetic elastomers, in particular blended with other rubbers such as SBR. The term mixture on the other hand means that the formulation can be prepared from pure polysulfanes of formula 1 (wherein x is other polysulfanes with x = 0, as defined in claim 1, if x is not zero).
그러나, 다른 한편으로 직접적으로 본 발명에 따르는 혼합물을 수득하기에 적합한 제조 공정을 사용하거나 다른 폴리설판을 가함으로써 배합물을 제조할 수 있음을 의미할 수 있다.On the other hand, however, it can mean that the formulation can be prepared by using a manufacturing process suitable for obtaining the mixture according to the invention or by adding another polysulfane.
본 발명에 따라, 혼합물은 주로 예를 들어 유럽 특허 제A-0 447 066호와 유럽 공개특허공보 제A-0620 250호에 기술되어 있는 바와 같이 실리카 함량을 상승시킨 타이어 트레드 배합물에 사용한다.According to the invention, the mixtures are mainly used in tire tread formulations with elevated silica content, as described, for example, in EP-A-0 447 066 and EP-A-0620 250.
본 발명에 따라, 혼합물을 사용하여 제조한 고무 배합물은 일반적으로 황 및/또는 황 공여체와 촉진제(가황 보조제)로 가황시킨다(여기서,황의 양은 일반적으로 0.1 내지 4phr이다).According to the present invention, rubber formulations prepared using the mixture are generally vulcanized with sulfur and / or sulfur donors and accelerators (vulcanization aids), where the amount of sulfur is generally 0.1 to 4 phr.
중합체 및 활성화제, 황산화제 및 가공 보조제와 같은 실제로 통상적인 첨가제 이외에 고무 배합물은 임의로 카본 블랙과 천연, 밝은 색의 충전제를 중합체 100부에 대해 10 내지 200부, 특히 25 재지 80부의 양으로 함유한다. 이러한 충전제는 BET 표면적이 1 내지 700m2/g, 특히 100 내지 250m2/g이고 또한 DBP 값이 150 내지 300㎖/100g인 것을 특징으로 한다.In addition to practically customary additives such as polymers and activators, sulfates and processing aids, the rubber blend optionally contains carbon black and natural, light colored fillers in an amount of 10 to 200 parts, in particular 25 to 80 parts per 100 parts of polymer. . These fillers are characterized by a BET surface area of 1 to 700 m 2 / g, in particular 100 to 250 m 2 / g and a DBP value of 150 to 300 ml / 100 g.
적합한 양태는 분말 뿐만 아니라 펠렛과 마이크로비드와 같은 저분진(low-dusting)형태이다. 본 발명에 따라, 여기서 혼합물의 양은 충전제 100부에 대해 0.5 내지 30부이다. 바람직하게는, 예를 들어 100 내지 250m2/g의 실리카를 일반적으로 사용하는 경우, 실리카 함량이 상승된 타이어 트레드 배합물과 같은 적용에서, 본 발명에 따라 혼합물을 충전제 100부에 대해 4 내지 10부의 양으로 사용한다.Suitable embodiments are powders as well as low-dusting forms such as pellets and microbeads. According to the invention, the amount of the mixture here is from 0.5 to 30 parts with respect to 100 parts of filler. Preferably, for example in the case of generally using 100 to 250 m 2 / g of silica, in applications such as tire tread blends with elevated silica content, the mixture is prepared according to the invention from 4 to 10 parts with respect to 100 parts of filler. Use in quantity.
본 발명에 따라, 혼합물을 동일 반응계 내에서 화합물에 혼입시키거나 향상된 양태에 있어서는 먼저 카본 블랙과 혼합한다. 예를 들어 독일 특허 제19609619.7호에 기술되어 있는 충전제로서 사용되는 실리카를 전개질시키는 것도 가능하다.According to the invention, the mixture is incorporated into the compound in situ or in the improved embodiment first with carbon black. It is also possible to develop silica, for example used as filler, as described in German Patent No. 19609619.7.
특히 오가노실란과 배합하여 충전시킨 고 실리카의 제조방법에 지대한 관심을 기울이고 있다. 적합한 방법은 유럽 출원 제0 447 066A1호에 기술되어 있으며, 여기서, TESPT를 사용하기 때문에 앞에서 언급한 스코칭되지 않도록 공정에서 배합동안 온도를 160℃를 초과하지 않도록 해야 한다. 그러나, 본 발명에 따르는 배합물을 사용하는 경우, 이러한 방해 효과가 없도록 하기 위해서는 160 내지 200℃, 특히 175 내지 190℃의 온도가 가능하다. 따라서 더 높은 배합기 온도를 선택할 수 있어서 실리카와 실란과의 반응을 촉진하여, 즉 배합시간 및/또는 배합단계의 횟수를 감소시킨다. 따라서 배합 조건을 매우 자유롭게 선택할 수 있다. 본 발명에 따라, 혼합물은 실질적으로 임의의 고무 제품을 사용한다. 이들은 특히 요구되는 특성을 향상시키기 위해서 일반적으로 실란의 양을 증가시키는 고 실리카 충전배합물(고무 100부에 대해 SiO2 40부 초과하는 양을 함유한다), 특히 타이어 트레드 배합물로 사용하기에 적합하다.Particular attention is paid to the preparation of high silica in combination with organosilane. A suitable method is described in EP 0 447 066A1, where the use of TESPT should ensure that the temperature does not exceed 160 ° C. during the formulation in the process so as to avoid the aforementioned scoping. However, when using the combinations according to the invention, in order to avoid such disturbing effects, temperatures of 160 to 200 ° C., in particular 175 to 190 ° C., are possible. A higher blender temperature can thus be selected to facilitate the reaction of silica with silane, ie reduce the blending time and / or the number of blending steps. Therefore, the mixing conditions can be selected very freely. According to the invention, the mixture uses substantially any rubber product. They are particularly suitable for use as high silica fillers (containing more than 40 parts of SiO2 per 100 parts of rubber), especially tire tread blends, which generally increase the amount of silane to improve the required properties.
이의 제조방법과 같이, 언급한 고무 배합물을 본 발명에 의해 제공한다.Like the preparation method thereof, the rubber compound mentioned is provided by the present invention.
황 및/또는 황 공여체와 촉진제로 가화시키고 천연 고무 또는 합성 고무, 밝은 색의 산화물(규산염)충전제, 임의의 카본 블랙 및 추가의 성분을 하나 이상 함유하는 고무 배합물의 제조방법은, 고무 성분들, 청구항1, 2 및 3항에 따르는 혼합물, 규산염 충전제 및 임의의 본 카본 블랙을 임의로 가소제, 화산화제 및 활성화제와 함께 혼련기[임의로 밴버리(Banbury) 내부 혼합기]에서, 160 내지 200℃에서 단일 단계 또는 다단계로 3 내지 15분 동안 혼련시킨 다음, 밴버리 내부 혼합기 또는 롤 분쇄기 속에서 가황 보조제를 60 내지 120℃, 바람직하게는 80 내지 110℃에서 가하고, 60 내지 120℃에서 추가로 2 내지 10분 동안 계속해서 배합한 다음 가공된 고무 배합물을 시트 또는 스트립으로 압연(壓延)한다.Processes for the preparation of rubber blends which are sulfurized and / or sulfur donors and accelerators and contain one or more of natural rubber or synthetic rubber, light colored oxide (silicate) fillers, optional carbon black and additional ingredients, include rubber components, The mixture, the silicate filler and any of the present carbon blacks according to claims 1, 2 and 3, optionally together with a plasticizer, a volcanizing agent and an activator, in a kneader (optionally a Banbury internal mixer), at a single stage at 160-200 ° C. Or kneading in multiple stages for 3 to 15 minutes, then adding the vulcanization aid at 60-120 ° C., preferably 80-110 ° C., at 60-120 ° C. for an additional 2-10 minutes in a Banbury internal mixer or roll mill. The compounding is then continued and the processed rubber compound is rolled into sheets or strips.
또한 본 발명은 오가노실란폴리설판 혼합물의 용도에 관한 것으로, 설판 쇄분포는 160 내지 200℃, 특히 175 내지 190℃의 온도 중에서 선택되며, 어떠한 가화되지 않은 배합물의 스코칭도 뚜렷하게 생기지 않는다.The present invention also relates to the use of organosilanepolysulfane mixtures, wherein the sulfane chain distribution is selected from temperatures between 160 and 200 ° C., in particular between 175 and 190 ° C., and no scouring of any unignited formulations occurs.
실제로, 이러한 스코칭은 가황되지 않은 시트 특성으로부터 평가하는데, 스코칭이 발생할수록 점점 거칠어지고 부스러지기 쉬워지고, 종종 롤 분쇄기로 처리할 수 없게 된다. 실험실에서 스코칭은 배합물의 점도를 측정하고 유동계 시험으로 가황되지 않은 화합물의 최소 토오크값을 결정함으로써 확인한다. 5무니 단위 이상, 특히 10무니 단위 이상의 더 낮은 온도(=더 신뢰할 수 있는 가공 거동)에서 배합한 조성물과 비교하여 점도에서 있어서 임의의 증가에 대한 안내값(quide value)은 배합물의 스코칭 지표로서 설정될 수 있다.Indeed, such scorching is evaluated from unvulcanized sheet properties, with the occurrence of scorching becoming more coarse and brittle and often incapable of processing with a roll mill. Scorching in the laboratory is confirmed by measuring the viscosity of the formulation and determining the minimum torque value of the unvulcanized compound by rheometer testing. The guide value for any increase in viscosity compared to compositions formulated at lower temperatures (= more than 10 Mooney units, in particular more than 10 Mooney units) is a scouring indicator of the formulation. Can be set.
실시예에서 사용한 시험 표준품Test Standards Used in Examples
300%모듈러스 MPa DIN 53 504300% Modulus MPa DIN 53 504
쇼어 A 경도 - DIN 53 505Shore A Hardness-DIN 53 505
DIN 마멸 ㎣ DIN 53 516DIN Wear ㎣ DIN 53 516
MTS DIN 53 513MTS DIN 53 513
무니 점도 DIN 53 523/53 524Mooney viscosity DIN 53 523/53 524
다음 화학물질은 실제 실시예에서 사용한다.The following chemicals are used in the practical examples.
Si 69 비스(트리에톡시실릴프로필)-Si 69 bis (triethoxysilylpropyl)-
테트라설판(Degussa AG)Tetrasulfane (Degussa AG)
부나(Buna) VLS 5025 1 HM 스티렌/부타디엔 고무, 용액 중합 공정을Buna VLS 5025 1 HM styrene / butadiene rubber for solution polymerization
사용하여 제조(Bayer AG)Manufactured Using (Bayer AG)
부나 CB 11S 폴리부타디엔 고무(Bayer AG)Buna CB 11S Polybutadiene Rubber (Bayer AG)
나프톨렌(Naftolen) ZD 방향족 가소제(Chemetal)Naphtolen ZD Aromatic Plasticizer (Chemetal)
불카녹스(Vulkanox) 4020 페닐렌디아민계 탈색Vulkanox 4020 Phenylenediamine Decolorization
황산화제(Baye AG)(6PPD)Sulfating agent (Baye AG) (6PPD)
보호제 G 35 오존 보호 왁스(Fuller)Protective Agent G 35 Ozone Protective Wax Fuller
불가시트(Vulkcit) D 디페닐구아니딘(Bayer AG)Vulkcit D diphenylguanidine (Bayer AG)
불가시트 CZ 벤조티아질-2-사이클로헥실설펜아미드Insoluble Sheet CZ Benzothiazyl-2-cyclohexylsulfenamide
(Bayer AG)(Bayer AG)
울트라실(Ultrasil) VN 3 GR BET 표면적이 175㎡/g인 침강 실리카Precipitated Silica with Ultrasil VN 3 GR BET Surface Area 175㎡ / g
(Degussa AG)(Degussa AG)
Si 266 비스(트리에톡시실릴프로필)디설판Si 266 bis (triethoxysilylpropyl) disulfane
Si 266 모드(mod) Si 266 mod
[실시예 1]Example 1
여러 오가노실란폴리설판 혼합물의 설판 쇄 분포 결정Determination of Sulfur Chain Distribution of Different Organosilane Polysulfane Mixtures
다음 조성물에 대한 HPSC로의 결정Determination by HPSC for the following compositions
[실시예 2]Example 2
180℃에서 유동계 곡선을 사용한 스코칭 결정Scorching Decision Using Flowmeter Curve at 180 ° C
실시예 1로부터의 모든 혼합물을 약 140℃에서 단계 1 및 2에 대한 배합물 조성물을 사용하여, 즉 가황 시스템이 없이, 실시예 3에 따르는 고무 배합물에 혼입시킨다. 이 가화되지 않은 화합물의 최소 토오크값을 180℃에서 유동계로 결정한다. 토오크값의 증가는 스코칭 거동을 지시한다(참조 : 제1도).All mixtures from Example 1 are incorporated into the rubber formulation according to Example 3 using the blend composition for steps 1 and 2 at about 140 ° C., ie without the vulcanization system. The minimum torque value of this uncalcified compound is determined by a rheometer at 180 ° C. Increasing the torque value indicates the scouring behavior (see Figure 1).
[실시예 3]Example 3
승용차 바퀴 배합물에서의 Si 69와 디설판 혼합물 사이의 가황되지 않은 화합물과 유동계 데이터의 비교Comparison of Rheological Data and Unvulcanized Compounds Between Si 69 and Disulfane Mixtures in Passenger Car Wheel Formulations
(Si 266 모드 : 57.7% S2, 31.4% S3, 8.3% S4, 2.3% S5, 0.2% S6)(Si 266 mode: 57.7% S2, 31.4% S3, 8.3% S4, 2.3% S5, 0.2% S6)
배합지시Formulation Instruction
단계 1Step 1
회전자 속도 : 70rpmRotor Speed: 70rpm
흐름 : 80℃Flow: 80 ℃
단계 2Step 2
회전자 속도 : 60rpmRotor Speed: 60rpm
흐름 : 80℃Flow: 80 ℃
단계 3Step 3
회전자 속도 : 60rpmRotor Speed: 60rpm
흐름 : 80℃Flow: 80 ℃
배합 지시Formulation instructions
단계 1Step 1
회전자 속도 : 95rpmRotor Speed: 95rpm
흐름 : 80℃Flow: 80 ℃
단계 2Step 2
회전자 속도 : 60rpmRotor Speed: 60rpm
흐름 : 80℃Flow: 80 ℃
단계 3Step 3
회전자 속도 : 30rpmRotor Speed: 30rpm
흐름 : 50℃Flow: 50 ℃
배합지시Formulation Instruction
단계 1Step 1
회전자 속도 : 115rpmRotor Speed: 115rpm
흐름 : 95℃Flow: 95 ℃
단계 2Step 2
회전자 속도 : 60rpmRotor Speed: 60rpm
흐름 : 80℃Flow: 80 ℃
단계 3Step 3
회전자 속도 : 30rpmRotor Speed: 30rpm
흐름 : 50℃Flow: 50 ℃
산출 온도를 180℃로 상승시켜 스코칭되는 위험없이 Si 266 모드로 가능하며, 이런 식으로 수득된 가황 고무 데이터를 산출 온도 140℃에서의 Si 69의 결과와 비교하였다.The temperature of the output was raised to 180 ° C. in Si 266 mode without the risk of scorching, and the vulcanized rubber data obtained in this way was compared with the results of Si 69 at the output temperature of 140 ° C.
Si 266 모드는 특히 0℃에서의 우수한 탄젠트 δ값으로 구별되어지고, 타이어 습윤 미끄럼 특징을 향상시킨다.The Si 266 mode is distinguished in particular by the good tan δ value at 0 ° C. and improves tire wet slip characteristics.
제2도는 Si 266 모드가 모든 배합 온도에서 확실하게 향상된 스코칭 거동을 보임을 나타내고, 제3도는 Si 266 모드가 Si 266 모드와 비교하여 확실하게 더 향상된 가황 시간을 보임을 나타내며, 제4도는 상승된 배합 온도에서도 Si 266 모드가 스코칭을 전혀 나타내지 않음으로 해서 확실하게 더 향상된 가공 거동을 가짐을 나타내고, 제5도는 Si 266 모두가 주입 속도에서 확실하게 유리함을 나타낸다.FIG. 2 shows that the Si 266 mode exhibits significantly improved scorching behavior at all blending temperatures, FIG. 3 shows that the Si 266 mode exhibits significantly improved vulcanization time compared to the Si 266 mode, and FIG. Even at the compounding temperature indicated, the Si 266 mode shows no scorching at all, indicating that it has a significantly improved processing behavior, and FIG. 5 shows that all of Si 266 is reliably advantageous at the implantation rate.
본 발명은 가화되지 않은 고무 배합물, 즉 가황에 필요한 황 또는 촉진제를 함유하지 않는 가화성 고무 배합물의 제조 동안 발생할 수 있는 승온에서의 스코칭이 발생되지 않는 오가노실란폴리설판 혼합물을 제공한다.The present invention provides an organosilane polysulfane mixture in which no scouring at elevated temperatures occurs during the preparation of an unvulcanized rubber blend, ie a flammable rubber blend that does not contain the sulfur or promoter required for vulcanization.
Claims (8)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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DE19628904 | 1996-07-18 | ||
DE19628904.1 | 1996-07-18 | ||
DE19702046A DE19702046A1 (en) | 1996-07-18 | 1997-01-22 | Mixtures of organosilane polysulfanes and a process for the preparation of rubber blends containing these blends |
DE19702046.1 | 1997-01-22 |
Publications (2)
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KR980009354A true KR980009354A (en) | 1998-04-30 |
KR100527607B1 KR100527607B1 (en) | 2006-03-14 |
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KR1019970033564A KR100527607B1 (en) | 1996-07-18 | 1997-07-18 | Mixture of organosilanepolysulphanes and a process for the production of rubber compounds containing these mixitures |
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KR (1) | KR100527607B1 (en) |
AR (1) | AR007733A1 (en) |
DE (2) | DE19702046A1 (en) |
MY (1) | MY141462A (en) |
UA (1) | UA44755C2 (en) |
YU (1) | YU49160B (en) |
ZA (1) | ZA976349B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20000020407A (en) * | 1998-09-21 | 2000-04-15 | 홍건희 | Rubber composition for tire belt |
KR100699183B1 (en) * | 1998-06-10 | 2007-03-27 | 데구사 게엠베하 | An oligomeric organosilanepolysulfane, a process for preparing the same and rubber mixtures and moulded articles containing the same |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19858863A1 (en) * | 1998-12-19 | 2000-06-21 | Degussa | Rubber compounds containing organosilane polysulfanes |
DE19916498A1 (en) * | 1999-04-12 | 2000-10-19 | Degussa | Silane mixture, useful for the production of vulcanized rubber compositions, has a polysulfane content of less than 20 %. |
US6452034B2 (en) | 2000-01-04 | 2002-09-17 | Crompton Corporation | Low-sulfur polysulfide silanes and process for preparation |
US6518335B2 (en) | 2000-01-05 | 2003-02-11 | Crompton Corporation | Sulfur-containing silane coupling agents |
DE10015308A1 (en) * | 2000-03-28 | 2001-10-11 | Degussa | Rubber mixture, useful for production of pneumatic tires, tubing and drive belts, comprises at least one rubber, a silicate filler, an organopolysulfone silane, an aminosilane and an alkylsilane |
US6359046B1 (en) | 2000-09-08 | 2002-03-19 | Crompton Corporation | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions |
US6635700B2 (en) | 2000-12-15 | 2003-10-21 | Crompton Corporation | Mineral-filled elastomer compositions |
US7968635B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
US7968633B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
US7696269B2 (en) | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
US7960460B2 (en) | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
US7781606B2 (en) | 2006-12-28 | 2010-08-24 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
US8592506B2 (en) | 2006-12-28 | 2013-11-26 | Continental Ag | Tire compositions and components containing blocked mercaptosilane coupling agent |
US7687558B2 (en) | 2006-12-28 | 2010-03-30 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
US7968634B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated core polysulfides |
US7737202B2 (en) | 2006-12-28 | 2010-06-15 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
US7968636B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated cyclic core polysulfides |
Family Cites Families (2)
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US5466848A (en) * | 1994-09-28 | 1995-11-14 | Osi Specialties, Inc. | Process for the preparation of silane polysulfides |
US5489701A (en) * | 1994-09-28 | 1996-02-06 | Osi Specialties, Inc. | Process for the preparation of silane polysulfides |
-
1997
- 1997-01-22 DE DE19702046A patent/DE19702046A1/en not_active Ceased
- 1997-07-02 DE DE59708357T patent/DE59708357D1/en not_active Revoked
- 1997-07-08 AR ARP970103045A patent/AR007733A1/en active IP Right Grant
- 1997-07-16 MY MYPI97003220A patent/MY141462A/en unknown
- 1997-07-17 UA UA97073824A patent/UA44755C2/en unknown
- 1997-07-18 YU YU30797A patent/YU49160B/en unknown
- 1997-07-18 KR KR1019970033564A patent/KR100527607B1/en not_active IP Right Cessation
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Cited By (2)
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KR100699183B1 (en) * | 1998-06-10 | 2007-03-27 | 데구사 게엠베하 | An oligomeric organosilanepolysulfane, a process for preparing the same and rubber mixtures and moulded articles containing the same |
KR20000020407A (en) * | 1998-09-21 | 2000-04-15 | 홍건희 | Rubber composition for tire belt |
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Publication number | Publication date |
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YU49160B (en) | 2004-03-12 |
DE59708357D1 (en) | 2002-11-07 |
AR007733A1 (en) | 1999-11-10 |
YU30797A (en) | 1999-07-28 |
MY141462A (en) | 2010-04-30 |
ZA976349B (en) | 1998-02-03 |
DE19702046A1 (en) | 1998-01-22 |
KR100527607B1 (en) | 2006-03-14 |
UA44755C2 (en) | 2002-03-15 |
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