CN1273975A - 新型低聚有机硅烷聚硫烷及其在橡胶和模塑制品中的应用 - Google Patents
新型低聚有机硅烷聚硫烷及其在橡胶和模塑制品中的应用 Download PDFInfo
- Publication number
- CN1273975A CN1273975A CN99108031A CN99108031A CN1273975A CN 1273975 A CN1273975 A CN 1273975A CN 99108031 A CN99108031 A CN 99108031A CN 99108031 A CN99108031 A CN 99108031A CN 1273975 A CN1273975 A CN 1273975A
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- China
- Prior art keywords
- polysulphideane
- organosilylane
- plymer
- rubber
- low
- 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.)
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- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明涉及低聚有机硅烷聚硫烷,它是由三种结构单元A和/或B和/或C构成的。其中Y=H,CN,-(CH2)nSiRR1R;R,R1,R2和R3各自表示H,(C1-C4)烷基,(C1-C4)烷氧基,卤素或O SiR1R2R3基团;x、z的统计平均值分别是1—6,2—6;n是1—8;o,p和q各自是1—40的正整数,o+p+q≥2和< 40;其前提条件是存在至少一种结构单元A或B,和该聚硫烷在橡胶及模塑制品尤其气胎的应用。
Description
本发明涉及新型低聚有机硅烷聚硫烷,它们的制备方法和它们在橡胶混合物和制备模塑制品中的应用。
现已知道的是含硫的有机硅化合物如3-巯基丙基三甲氧基硅烷或双(3-[三乙氧基甲硅烷基]-丙基)四硫烷能够在氧化物填充的橡胶混合物中用作硅烷键接剂或增强剂,尤其用于汽车轮胎的胎面和其它部件(DE2141 159,DE2 212 239,US 3 978 103,US4 048 206)。
EP 0 784 072公开了一种基于至少一种弹性体和硅石填料和增强添加剂的橡胶混合物,它是通过混合至少一种官能化聚有机硅氧烷化合物或由后者“原位”生产出的反应产物而制备的,并且它含有官能化有机硅烷作为其它组分。使用的单体结构单元尤其是3-巯基丙基三烷氧基硅烷或双(三烷氧基-甲硅烷基丙基)四硫烷,各自含有3个或6个烷氧基取代基。
此外,现已知的是含硫的硅烷键接剂是在密封化合物、浇铸金属用的铸型、色料和保护涂料、粘合剂、沥青混合物和氧化物填充的塑料的制备过程中使用。
最后,可能的应用包括活性物质和官能化单元在无机载体材料上的固定,例如在固定均相催化剂和酶时,和在制备固定床催化剂时及用于液相色谱时。
当用有机硅烷和填料如沉淀硅石制备橡胶混合物时,在第一混合过程中,例如在密炼机中发生化学反应。该化学反应由有机硅烷和填料之间的缩合反应组成,同时释放出大量的醇。这些释放出来的醇有时候在橡胶混合物的进一步加工中引起突出的技术问题,如在挤出过程中混合物的孔隙度或在橡胶本身中产生不希望得到的气泡。此外,出于健康和环境的原因希望降低在反应过程中释放的醇量。
现已发现,现有技术中的这些缺点能够通过使用低聚有机硅烷聚硫烷代替目前所使用的单体含硫化合物而大大避免。
因此,本发明提供了一种根据权利要求1的新型低聚有机硅烷聚硫烷,其中低聚有机硅烷聚硫烷是由三种结构单元A和/或B和/或C构成的:其中Y=H,CN,-(CH2)nSiRR1R2;
R,R1,R2和R3各自表示H,(C1-C4)烷基,(C1-C4)烷氧基,卤素或OSiR1R2R3基团;
x的统计平均值是1-6,
z的统计平均值是2-6,
n是1-8,
o,p和q各自是1-40中的正整数,其中o+p+q可以≥2和<40,前提条件是至少一种结构单元A或B存在于低聚有机硅烷聚硫烷中。
上述类型的优选低聚有机硅烷聚硫烷是由三种结构单元A和/或B和/或C构成:
其中Y,R,R1,R2,R3,x,z和n与以上给出的定义相同,以及o,p和q各自是1-20中的正整数,其中o+p+q可以≥2和<20,前提条件是存在至少一种结构单元A或B。
本发明的低聚有机硅烷聚硫烷可通过Y基团被设计成环状、支链或直链。
本发明的化合物可以是具有确定分子量的化合物或具有一定分子量范围内的低聚物混合物。由于工艺方面的原因,低聚物混合物的制备一般比较简单而被采纳。化合物具有在约800-16000g/mol范围内的分子量。本发明的低聚有机硅烷聚硫烷优选具有约800-5000g/mol的分子量。
本发明的低聚有机硅烷聚硫烷尤其是由结构单元B和C构成,它是通过合适聚硫烷和有机硅烷的共聚合反应获得。
本发明的低聚有机硅烷聚硫烷可通过任何两种烷氧基甲硅烷基结构单元的缩合制备。在上述取代基类型的范围内,任何含硫的有机硅化合物可以自身低聚合或与另一种含硫或非含硫的有机硅化合物共聚合。为了制备本发明的低聚有机硅烷聚硫烷,下面结构类型(I)的单体化合物:其中Y=H,CN,-(CH2)nSiRR1R2;
R,R1和R2各自表示H,(C1-C4)烷基,(C1-C4)烷氧基,卤素或OSiR1R2R3基团;x的统计平均值可能是1-6;选择性地在溶剂中和/或选择性地借助于催化剂,在0℃-150℃之间的反应温度和添加水的情况下发生自聚合或者在类似的反应条件下与结构类型(II)的化合物进行共聚合反应:
RR1R2R3Si (II)
其中R,R1,R2和R3各自表示H,(C1-C4)烷基,(C1-C4)烷氧基,卤素或OSiR1R2R3基团。
下面给出了适合于本发明中的反应的一些(含硫)有机硅化合物的实例:
双-(3-[三乙氧基甲硅烷基]-丙基)四硫烷,3-硫代氰酸根丙基三乙氧基硅烷,3-巯基丙基三甲氧基硅烷,丙基三乙氧基硅烷,辛基三乙氧基硅烷,十六烷基三乙氧基硅烷,二甲基二乙氧基硅烷,3-巯基丙基三乙氧基硅烷,双-3-三乙氧基甲硅烷基丙基二硫烷,双-3-三乙氧基甲硅烷基丙基三硫烷。
缩合反应通过添加水来进行且同时除去醇,并可以在本体或在惰性有机溶剂或其混合物中进行,例如在芳族溶剂如氯苯中,在卤代烃如氯仿或二氯甲烷中,在醚如二异丙基醚,叔丁基甲基醚,四氢呋喃或乙醚中,在乙腈中或在羧酸酯如乙酸乙酯、乙酸甲酯或乙酸异丙酯中或在醇如甲醇、乙醇、正丙醇、异丙醇、正丁醇、仲丁醇或叔丁醇中。优选的溶剂是乙醇或乙酸乙酯。该反应可催化进行。催化剂按催化量或化学计量用量添加。在烷氧基硅烷的溶胶—凝胶化学(SOLGEL chemistry)领域的熟练人员已知的任何酸性、碱性或亲核催化剂(参见,例如,R.Corriu,D.Leclercq,应用化学(Angew.Chem.),1996,108,1524-1540)都适合于本发明中的低聚反应。不管催化剂是存在于与反应溶液相同的相中(均相催化)还是以固体存在(非均相催化)以及在反应结束后的分离上都没有太大的差别。、
使用路易斯酸例如原钛酸四丁基酯的均相催化或使用氟化铵的亲核催化或使用氧化铝的非均相催化是特别合适的。碱性催化例如可用有机碱如三乙基胺,四甲基哌啶,四丁基胺或吡啶进行或用无机碱如NaOH,KOH,Ca(OH)2,Na2CO3,K2CO3,CaCO3,CaO,NaHCO3,KHCO3或醇盐如甲醇钠或乙醇钠进行。亲核催化可用任何氟化物,例如氟化铵、氟化钠、氟化钾或任何四烷基氟化铵如四丁基氟化铵来进行。酸催化可用含水的稀无机酸或路易斯酸在水中的溶液来进行。用含水的稀NaOH溶液或氟化铵在水中的溶液进行催化是优选的,其中使用占所添加水量的1mol%的催化剂。反应条件,尤其水的添加量,经选择后使反应产物不致于缩聚得到固体。在反应结束后,按照本领域熟练人员已知的方法除去易挥发的组分而且以常规方式将催化剂钝化或除去。
术语“烷基”被理解为包括“直链”和“支链”烷基。“直链烷基”被理解成诸如甲基、乙基、正丙基、正丁基、正戊基和正己基的基团,“支化烷基”被理解成诸如异丙基或叔丁基的基团。术语“卤素”被理解为意指氟,氯,溴或碘。术语“烷氧基”被理解为包括诸如甲氧基,乙氧基,丙氧基,丁氧基,异丙氧基,异丁氧基或戊氧基。
对于与取代基相关数据的情况,如(C1-C4)烷氧基,下标的数字给出了该基团中所有的碳原子数。
在实施例1-4中,以举例的方式描述了本发明的低聚有机硅烷聚硫烷的制备方法。
本发明还提供含有新型低聚有机硅烷聚硫烷作为键接剂或增强助剂的橡胶混合物以及在硫化步骤之后得到的模塑制品,尤其气胎或轮胎胎面,它们在实施本发明的方法之后具有低滚动阻力和同时具有良好的湿抓握性能和高耐磨损性。
因此本发明提供一种橡胶混合物,它含有橡胶,填料,尤其沉淀硅石,和选择性的其它橡胶助剂,和至少一种由上述结构单元构成的并以相当于橡胶用量的0.1-15wt%的量使用的低聚有机硅烷聚硫烷。
在橡胶混合物中不可接受的醇的释放可通过使用本发明的低聚有机硅烷聚硫烷大大减少,这归因于早已发生的预缩合反应。与常规的操作模式相比,例如简单地通过使用双(3-[三乙氧基甲硅烷基]-丙基)四硫烷(TESPT)作为键接剂,醇的释放可减少约30%(参见实施例1-4)。
另外令人惊奇地发现,用低聚硅烷制备的橡胶混合物和从该混合物制得的橡胶硫化物优越于用单体硅烷按常规方法制得的其它橡胶混合物。这尤其通过对于所生产的橡胶硫化物的静态和动态性能各个特征的改进来体现。从而得到增高的拉伸强度,降低的落球回弹率(在0℃)和提高的tanδ(在0℃)值(也参见表3-5)。这使轮胎改进了湿抓握能力。令人惊奇地,这一改进无需在损失滚动阻力(与60℃下的tanδ相关)的情况下就能够实现。
用于橡胶混合物中的特别优选的低聚物是含有50-85%的结构单元A和B的那些,其中Y=(CH2)nSiRR1R2,n=3以及R,R1和R2=OC2H5(通过使用1H-NMR谱由OC2H5的残余含量测定),其中x和z的统计平均值是2-4。
添加本发明的低聚有机硅烷聚硫烷和添加填料优选在100-200℃的物料温度下进行,也可以在更低的温度(40-100℃)下进行,例如与其它橡胶助剂一起。
低聚有机硅烷聚硫烷可以在混合过程中以纯净形式或以吸附在惰性有机或无机载体上的形式添加。优选的载体材料是硅石,天然或合成硅酸盐,氧化铝或炭黑。
下面的填料适合用于本发明的橡胶混合物中:—炭黑:这里所使用的炭黑是通过灯黑、炉法炭黑或槽法炭黑方法制备并具有20-200m2/g的BET表面积,如SAF,ISAF,HSAF,HAF,FEF或GPF炭黑。选择性地,炭黑还可含有杂原子如Si。—高分散性硅石,例如通过硅酸盐溶液的沉淀或卤化硅的火焰水解制得,具有比表面积5-1000,优选20-400m2/g(BET表面积)和初始粒子直径为10-400nm。选择性地,硅石还可以与其它金属氧化物如Al、Mg、Ca、Ba、Zn和Ti的氧化物一起作为混合氧化物形式存在。—合成硅酸盐,如硅酸铝,碱土金属硅酸盐如硅酸镁或硅酸钙,BET表面积为20-400m2/g和初始粒子直径为10-400nm。—天然硅酸盐,如高岭土和其它天然存在的硅酸盐。—玻璃纤维和玻璃纤维产品(毡,绳)或玻璃微珠。
BET表面积为20-400m2/g的炭黑或从硅酸盐溶液沉淀制得的、BET比表面积为20-400m2/g的高分散性硅石,优选以5-150重量份的量使用,各重量份相对于100重量份橡胶。
所提及的填料可以单独或作为混合物使用。在该方法的一个特别优选实施方案中,10-150重量份的浅白色填料,选择性地与0-100重量份炭黑一起,和0.3-10重量份的通式(I)化合物用于制备混合物,各重量份相对于100重量份橡胶。
除了天然橡胶外,合成橡胶也适合制备本发明的橡胶混合物。优选的合成橡胶例如在W.Hofmann,橡胶技术(Kautschuktechnologie),Genter Verlag,Stuttgart,1980中描述的那些。它们特别包括:-聚丁二烯(BR)-聚异戊二烯(IR)-苯乙烯/丁二烯共聚物,苯乙烯含量为1-60,优选2-50wt%(SBR)-异丁烯/异戊二烯共聚物(IIR)-丁二烯/丙烯腈共聚物,丙烯腈含量为5-60,优选10-50wt%(NBR)一部分氢化或全氢化NBR橡胶(HNBR)-乙烯/丙烯/二烯共聚物(EPDM)以及这些橡胶的混合物。玻璃化转变温度高于-50℃的阴离子聚合S-SBR橡胶和它们与二烯橡胶的混合物对于制备车辆轮胎来说是理想的。
本发明的橡胶硫化物可含有其它橡胶助剂如反应促进剂,抗老化剂,热稳定剂,光稳定剂,抗臭氧剂,加工助剂,增塑剂,增粘剂,发泡剂,色料,颜料,蜡,增量剂,有机酸,阻滞剂,金属氧化物和活化剂如三乙醇胺,聚乙二醇,己三醇,它们在橡胶工业中是熟知的。
橡胶助剂以常规量使用,这主要决定于最终的用途。常规量例如是相当于橡胶的0.1-50wt%。低聚硅烷也可用作单一的交联剂。通常建议另添加其它交联剂。硫或过氧化物可用作已知的其它交联剂。本发明的橡胶混合物还可含有硫化促进剂。合适的硫化促进剂例子是巯基苯并噻唑,磺酰胺,胍,秋兰姆,二硫代氨基甲酸酯,硫脲和硫代碳酸酯。硫化促进剂和硫或过氧化物以相当于橡胶的0.1-10wt%、优选0.1-5wt%的量使用。
本发明的橡胶混合物的硫化可在100-200℃,优选130-180℃,选择性地在10-200巴压力下进行。在橡胶中混入填料、选择性的橡胶助剂和本发明的低聚硅烷(I)的过程可在普通混合装置如辊炼机、密炼机和混合挤出机中进行。本发明的橡胶硫化物适合生产模塑制品,例如生产气胎,轮胎胎面,电缆护套,软管,驱动带,传输带,辊涂层,轮胎,鞋底,密封环和减震元件。
实施例1-4:低聚有机硅烷聚硫烷的制备实施例1:
在80℃和搅拌下将266克(0.5mol)的双-(3-[三乙氧基甲硅烷基]-丙基)四硫烷(TESPT,Degussa AG)最初与1ml的原钛酸四丁基酯首先引入到500ml圆底烧瓶中。然后,将调和在10ml分析纯乙醇中的6.75克(0.38mol)水在搅拌下缓慢加入。在加料过程结束之后,在80℃下搅拌继续进行1小时,然后在80℃和500-300mbar下蒸馏出乙醇。然后,在80℃/30mbar下除去剩余的挥发性组分。获得了具有2.38个乙氧基/每个Si单元(从1H-NMR谱得到)和在燃烧之后有25.0%残余物的油状黄色产物。实施例2:
在80℃和搅拌下将133克(0.25mol)TESPT与1ml原钛酸四丁基酯和100ml分析纯乙醇一起加入到500ml圆底烧瓶中。然后将调和在10ml分析纯乙醇中的5.40克(0.30mol)水在搅拌下缓慢地加入。其它的制备过程如实施例1中所述。获得了具有2.08个乙氧基/每个Si单元(从1H-NMR谱得到)和在燃烧之后有25.8%残余物的油状黄色产物。实施例3:
按照与实施例1中相同的方法完成制备过程。133克(0.25mol)TESPT和44.0克(0.21mol)丙基三乙氧基硅烷(PTES)用作反应物。水的添加量是8.50克(0.47mol)。获得了仅具有1.85个乙氧基/每个Si单元(从1H-NMR谱得到)和在燃烧之后有28.8%残余物的油状产物。实施例4:
按照与实施例3中相同的方法完成制备过程,改变之处在于,代替PTES,使用31.0克(0.21mol)的二甲基二乙氧基硅烷(DMDES,Gelest)。根据1H-NMR的测定,获得了具有1.60个乙氧基/每个Si单元的油状产物,在燃烧之后有30.3%残余物。实施例5-11:橡胶混合物和硫化物的制备
所使用的一般方法
在密炼机(Werner & Pfleiderer GK1.5N)中按两步方法制备橡胶混合物,混合时间为6和5分钟,转速为70rpm,出料温度至多为155℃,随后根据下表1中给出的配方,在至多为90℃的温度下在密炼机中进行混合阶段。单位“phr”是指相对于100重量份所使用的原料生橡胶来说的重量份数。
制备橡胶混合物和它们的硫化物的一般方法例如描述在“橡胶技术手册(Rubber Technology Handbook)”,W.Hofmann,Hanser Verlag,1994年。
试样的硫化时间是在165℃下60分钟。
表1
物质 量[phr] |
第一阶段 |
Buna VSL 5025-1 96.0Buna CB 24 30.0Ultrasil VN3 80.0ZnO 3.0硬脂酸 2.0Naftolene ZD 10.0Vulkanox 4020 1.5Protector G35P 1.0TESPT 6.4 |
第二阶段 |
间歇阶段1 |
第三阶段 |
间歇阶段2Vulkacit D 2.0Vulkacit CZ 1.5硫 1.5 |
VSL 5025-1聚合物是购自Bayer AG的溶液聚合的SBR共聚物,其苯乙烯含量为25wt%和丁二烯含量为75wt%。73%的丁二烯是1,2-连接,10%是顺式-1,4-连接和17%是反式-1,4-连接。共聚物含有37.5phr的油并且具有门尼粘度(ML 1+4/100℃)为约50。
Buna CB24聚合物是购自Bayer AG的顺式-1,4-聚丁二烯(钛型),顺式-1,4-含量为92%,反式-1,4-含量为4%,1,2-连接方式含量为4%,门尼粘度在44和50之间。
购自Gegussa AG的VN3硅石具有的BET表面积为175m2/g。
TESPT(双-3-[三乙氧基甲硅烷基]-丙基)四硫烷)是由Degussa AG以商品名Si 69销售。
购自Chemetall的Naftolen ZD用作芳族油;Vulkanox 4020是购自Bayer AG的PPD,Protektor G35P是购自HB-Fuller GmbH的抗臭氧蜡。Vulkacit D(DPG)和Vulkacit CZ(CBS)是购自Bayer AG的商品。
橡胶工程性能的测试是根据表2中给出的试验方法进行的。
表2
实施例5,6和7:
物理测试 标准/条件 |
ML1+4,100℃ DIN 53523/3,ISO 667 |
Vulcameter试验,165℃ DIN 53529/3,ISO6502 |
环拉伸试验,23℃ DIN 53504,ISO37 |
拉伸强度模量断裂伸长 |
肖氏A硬度,23℃ DIN 53 505 |
落球回弹率,0和60℃ ASTM D 5308 |
粘弹性 DIN 53 513,ISO28560和60℃E*tanδ |
DIN磨损,10N力 DIN 53 516 |
分散 ISO/DIN 11345 |
根据下面所述的一般方法进行实施例5(对比例),6和7。
不同于实施例5,代替6.4phr TESPT,在实施例6和7的混合物中使用6.1phr的来自实施例1和实施例2的低聚硅烷。下面给出原始混合料和其硫化物的橡胶数据:
表3
实施例8(对比例):
实施例 | 5 | 6 | 7 | |
特征: | 单位: | TESPT | 实施例1的低聚硅烷 | 实施例2的低聚硅烷 |
原始混合料结果 | ||||
ML(1+4),100℃Dmax-Dmint 10%t 90% | [ME][dNm][min][min] | 6617.11.9430.11 | 6817.351.8134.57 | 6716.971.831.89 |
硫化产物结果 | ||||
拉伸强度模量100%模量300%断裂伸长 | [MPa][MPa][MPa][%] | 14.02.411.2340 | 11.52.511.5300 | 14.22.511.5350 |
肖氏A硬度 | [SH] | 65 | 66 | 65 |
落球回弹率(0℃)落球回弹率(60℃) | [%][%] | 11.162.1 | 10.664.0 | 10.763.1 |
DIN磨损 | [mm3] | 86 | 87 | 84 |
动态屈服模量E*(0℃)动态屈服模量E*(60℃)损耗因子tanδ(0℃)损耗因子tanδ(60℃) | [MPa][MPa][-][-] | 23.29.70.4810.111 | 21.89.10.4800.110 | 23.69.30.4890.115 |
不同于实施例5,用4.8phr TESPT和1.6phr PTES的混合物代替6.4phr TESPT。这一混合物和其相应硫化物的橡胶数据与实施例9的橡胶数据在表4中进行比较。实施例9:
不同于对比例8,使用实施例3的低聚硅烷来代替TESPT和PTES的混合物。原始混合料和其硫化产物的橡胶数据在下面给出:
表4
实施例10(对比例):
实施例 | 8 | 9 | |
特征: | 单位: | TESPT和PTES的混合物 | 实施例3的低聚硅烷 |
原始混合料结果 | |||
ML(1+4),100℃ | [ME] | 63 | 65 |
Dmax-Dmint 10%t 90% | [dNm][min][min] | 17.352.0928.09 | 18.911.9224.34 |
硫化产物结果 | |||
拉伸强度模量100%模量300%断裂伸长 | [MPa][MPa][MPa][%] | 14.92.511.2360 | 14.12.712.5330 |
肖氏A硬度 | [SH] | 66 | 66 |
落球回弹率(0℃)落球回弹率(60℃) | [%][%] | 10.662.8 | 10.163.2 |
DIN磨损 | [mm3] | 92 | 89 |
动态屈服模量E*(0℃)动态屈服模量E*(60℃)损耗因子tanδ(0℃)损耗因子tanδ(60℃) | [MPa][MPa][-][-] | 23.69.30.4890.112 | 25.59.80.4960.105 |
不同于对比例5,使用5.2phr TESPT和1.2phr DMDES的混合物来代替6.4phr TESPT。这一混合物和其相应硫化物的橡胶数据与实施例11的橡胶数据在表5中进行比较。实施例11:
不同于对比例10,使用6.1phr实施例4的低聚硅烷来代替TESPT和DMDES的混合物。下面给出原始混合料和其硫化产物的橡胶数据(表5):
表5
实施例 | 10 | 11 | |
特征: | 单位: | TESPT和DMDES的混合物 | 实施例4的低聚硅烷 |
原始混合料结果 | |||
ML(1+4),100℃ | [ME] | 66 | 66 |
Dmax-Dmint 10%t 90% | [dNm][min][min] | 17.782.1227.9 | 18.21.8625.4 |
硫化产物结果 | |||
拉伸强度模量100%模量300%断裂伸长 | [MPa][MPa][MPa][%] | 11.52.411.0310 | 15.62.611.7360 |
肖氏A硬度 | [SH] | 66 | 66 |
落球回弹率(0℃)落球回弹率(60℃) | [%][%] | 10.861.5 | 10.563.0 |
DIN磨损 | [mm3] | 87 | 92 |
动态屈服模量E*(0℃)动态屈服模量E*(60℃)损耗因子tanδ(0℃)损耗因子tanδ(60℃) | [MPa][MPa][-][-] | 25.59.70.4810.111 | 24.49.30.5000.111 |
Claims (17)
2、根据权利要求1的低聚有机硅烷聚硫烷,其特征在于该有机硅烷聚硫烷含有50-85%的两种结构单元A和B,其中Y=-(CH2)nSiRR1R2,R=R1=R2=乙氧基,n=3,其中x和z的统计平均值是2-4。
3、根据权利要求1或2中一项的低聚有机硅烷聚硫烷,其特征在于它们由结构单元B和C组成,其中R,R1,R2,R3,n,z,p和q与权利要求1中的定义相同。
4、根据前述权利要求中任何一项的低聚有机硅烷聚硫烷,其特征在于它们是不同链长的有机硅烷聚硫烷的混合物。
6、根据权利要求5的方法,其特征在于双(3-[三乙氧基甲硅烷基]丙基)四硫烷作为含硫的有机硅化合物与丙基三乙氧基硅烷或二甲基乙氧基硅烷进行共聚合。
7、通过权利要求5或6的方法获得的低聚有机硅烷聚硫烷。
8、根据权利要求1-4或7中一项的低聚有机硅烷聚硫烷在橡胶混合物中的应用。
9、含有根据权利要求1-4或7中一项或多项的低聚有机硅烷聚硫烷的橡胶混合物。
10、根据权利要求9的橡胶混合物,其特征在于该有机硅烷聚硫烷的用量是相对于橡胶用量的0.1-15wt%。
11、根据权利要求9或10的橡胶混合物,其特征在于该有机硅烷聚硫烷含有50-85%的两种结构单元A和B,其中Y=-(CH2)nSiRR1R2,R=R1=R2=乙氧基,n=3,并且x和y的统计平均值是2-4。
12、根据前面权利要求9-11中一项或多项的橡胶混合物,其特征在于它们含有合成橡胶,硅石填料和由双-(3-[三乙氧基甲硅烷基]丙基)四硫烷进行聚合或由双-(3-[三乙氧基甲硅烷基]丙基)四硫烷和丙基三乙氧基硅烷进行共聚合得到的低聚有机硅烷聚硫烷。
13、制备一种除含有橡胶外还含有至少一种其它填料的橡胶混合物的方法,其特征在于:有权利要求1-4或7中任何一项的低聚有机硅烷聚硫烷存在。
14、从权利要求9-12之一的橡胶混合物获得的模塑制品。
15、根据权利要求14的模塑制品,其特征在于它是气胎。
16、根据权利要求14的模塑制品,其特征在于它是轮胎胎面。
17、根据权利要求9-12之一的橡胶混合物在生产模塑品,尤其是气胎或轮胎胎面中的用途。
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JP5910568B2 (ja) * | 2013-04-23 | 2016-04-27 | 信越化学工業株式会社 | 有機官能基含有オルガノポリシロキサンの製造方法 |
KR101572106B1 (ko) | 2013-08-20 | 2015-11-26 | 한국타이어 주식회사 | 타이어 트레드용 고무 조성물 및 이를 이용하여 제조한 타이어 |
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-
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- 1998-06-10 DE DE19825796A patent/DE19825796A1/de not_active Ceased
-
1999
- 1999-06-02 ES ES99110615T patent/ES2216376T3/es not_active Expired - Lifetime
- 1999-06-02 DE DE59909445T patent/DE59909445D1/de not_active Expired - Lifetime
- 1999-06-02 EP EP99110615A patent/EP0964021B1/de not_active Expired - Lifetime
- 1999-06-02 AT AT99110615T patent/ATE266694T1/de not_active IP Right Cessation
- 1999-06-02 PT PT99110615T patent/PT964021E/pt unknown
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- 1999-06-09 PL PL99333617A patent/PL333617A1/xx not_active Application Discontinuation
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- 1999-06-09 HU HU9901929A patent/HU221746B1/hu not_active IP Right Cessation
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- 1999-06-09 RU RU99113941/04A patent/RU2217446C2/ru not_active IP Right Cessation
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- 1999-06-10 CN CNB991080319A patent/CN1209365C/zh not_active Expired - Lifetime
- 1999-06-10 ID IDP990559D patent/ID22866A/id unknown
- 1999-06-10 UA UA99063220A patent/UA64732C2/uk unknown
- 1999-06-10 BR BR9902232-0A patent/BR9902232A/pt not_active Application Discontinuation
- 1999-06-10 KR KR1019990021578A patent/KR100699183B1/ko not_active IP Right Cessation
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Cited By (12)
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CN100381448C (zh) * | 2001-04-30 | 2008-04-16 | 通用电气公司 | 用于填充弹性体组合物的含杂化硅偶联剂 |
US7629430B2 (en) | 2001-04-30 | 2009-12-08 | Momentive Performance Materials Inc. | Hybrid silicon-containing coupling agents for filled elastomer compositions |
US7919650B2 (en) | 2006-02-21 | 2011-04-05 | Momentive Performance Materials Inc. | Organofunctional silanes and their mixtures |
CN101318971B (zh) * | 2008-03-17 | 2010-12-15 | 南京曙光硅烷化工有限公司 | 一种减少含硫硅烷中乙醇的方法 |
CN102439016A (zh) * | 2009-05-20 | 2012-05-02 | 米其林技术公司 | 有机硅偶联剂 |
CN102439016B (zh) * | 2009-05-20 | 2015-07-22 | 米其林集团总公司 | 有机硅偶联剂 |
CN103509190A (zh) * | 2012-06-27 | 2014-01-15 | 信越化学工业株式会社 | 有机聚硅氧烷及其制备方法 |
CN103509190B (zh) * | 2012-06-27 | 2017-05-24 | 信越化学工业株式会社 | 有机聚硅氧烷及其制备方法 |
CN105026481A (zh) * | 2013-02-25 | 2015-11-04 | 横滨橡胶株式会社 | 重负荷轮胎用橡胶组合物及充气轮胎 |
CN105026481B (zh) * | 2013-02-25 | 2017-08-22 | 横滨橡胶株式会社 | 重负荷轮胎用橡胶组合物及充气轮胎 |
CN106800571A (zh) * | 2017-01-17 | 2017-06-06 | 荆州市江汉精细化工有限公司 | 一种环状含硫硅烷低聚物及制备方法 |
CN106800571B (zh) * | 2017-01-17 | 2019-03-08 | 荆州市江汉精细化工有限公司 | 一种环状含硫硅烷低聚物及制备方法 |
Also Published As
Publication number | Publication date |
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DE59909445D1 (de) | 2004-06-17 |
MY118650A (en) | 2004-12-31 |
HUP9901929A2 (hu) | 1999-12-28 |
IL130312A (en) | 2005-06-19 |
RU2217446C2 (ru) | 2003-11-27 |
DE19825796A1 (de) | 1999-12-16 |
IL130312A0 (en) | 2000-06-01 |
JP4376999B2 (ja) | 2009-12-02 |
UA64732C2 (uk) | 2004-03-15 |
CA2273873A1 (en) | 1999-12-10 |
US6331605B1 (en) | 2001-12-18 |
ES2216376T3 (es) | 2004-10-16 |
EP0964021B1 (de) | 2004-05-12 |
PT964021E (pt) | 2004-09-30 |
HU9901929D0 (en) | 1999-08-30 |
EP0964021A2 (de) | 1999-12-15 |
PL333617A1 (en) | 1999-12-20 |
TR199901295A3 (tr) | 2000-01-21 |
ZA993900B (en) | 1999-12-10 |
EP0964021A3 (de) | 2001-09-26 |
KR100699183B1 (ko) | 2007-03-27 |
JP2000038395A (ja) | 2000-02-08 |
TW546326B (en) | 2003-08-11 |
HUP9901929A3 (en) | 2000-10-30 |
ID22866A (id) | 1999-12-16 |
ATE266694T1 (de) | 2004-05-15 |
BR9902232A (pt) | 2000-05-23 |
TR199901295A2 (xx) | 2000-01-21 |
CN1209365C (zh) | 2005-07-06 |
KR20000006080A (ko) | 2000-01-25 |
HU221746B1 (hu) | 2002-12-28 |
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