CN1025434C - 一种氟弹性体组合物 - Google Patents
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 17
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 15
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- 229910052736 halogen Inorganic materials 0.000 claims 1
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
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Abstract
用过氧化物固化含有溴或碘的氟弹体时会产生毒性很强的易挥发物质,如溴甲烷或碘甲烷或溴乙烷或碘乙烷。本发明通过在固化混合物中加入少量的能与产生上述毒性物质的自由基结合从而防止毒性物质形成的物质,来使固化时产生的毒性物质大大减少。加入的物质不含明显影响固化程度和固化产品的特性。
Description
用有机过氧化物固化下述氟弹性体是已知的技术,这里所说的氟弹性体是指聚合物链上和/或在聚合物两端含有作为固化位点的溴原子或碘原子的氟弹体。在所述的氟弹性体中,溴或碘是用下面方法引进到弹性体大分子中去的,即在聚合阶段用溴化或碘化的共聚单体,尤其如氟溴化烯烃、溴化或碘化的氟乙烯醚,或者在聚合时用溴化或碘化的化合物如链转移剂。
在过氧化物固化中,一般采用脂族或环脂族型有机过氧化物,或者采用饱和或不饱和的烷基芳族化合物的过氧化物,例如2,5-二甲基-2,5-二(叔丁基过氧化)己烯-3、2,5-二甲基-2,5-二(叔丁基过氧化)己烷、过氧化二枯基、过苯甲酸叔丁酯、3,3-二(叔丁基过氧化)丁酸乙酯以及1,1-二(叔丁基过氧)-3,3,5-三甲基环己烷。在固化过程中这些过氧化物会形成甲基或乙基的自由基。这些自由基与氟弹性体中所含的溴或碘结合时,就形成了上述的甲基或乙基的溴化物或碘化物,这些化合物毒性很强并且可能是致癌的挥发性物质。
因此,尽管用过氧化物固化含有溴或碘的氟弹性体所制得的固化产品至少某些性能比用离子固化氟弹性体的产物的性能优越,但是用过氧化物固化上述产品时会严重损害操作人员的健康,因而有关管理部门可能会很快就禁止这种作业。
因此,本发明的一个目的是克服上述的严重缺点,其方法是在固化
混合物中加入一种在固化过程中能大大减少散发出溴化或碘化甲基或乙基的物质。
事实上,已经意外地发现某些类型的物质以适当的量(一般为每100份重氟弹体加0.1至3份重)加入到固化混合物中可基本上减少所述有毒物质的散发,而不会明显改变固化程度和所得固化产物的特性。本发明添加剂的反应机理可能是基于下述事实:这些添加剂能与由有机过氧化物所产生的甲基或乙基自由基结合,从而形成可连续进行交联反应的新自由基,这样就防止了溴化或碘化甲基或乙基的形成。但是,仅仅基于这种设想还不能预见到任种物质真正适于用作本发明的添加剂。事实上,有许多物质确实能够与甲基和乙基的自由基结合,因而能大大地减少上述溴化物和碘化物的产生,但是这些物质对固化过程有不利的影响,会使固化过程变得非常慢,而且效率极低,同时所制得的固化产物质量非常差。
适于用作本发明添加剂的物质是属于下列类型的物质:
a)下式所示的苯并噻唑及其衍生物:
其中:X代表H、
特别是苯并噻唑、2-巯基苯并噻唑、二硫化苯并噻唑、吗啉-2-苯并噻唑硫酰胺、巯基苯并噻唑锌盐。
b)下式所示的马来酰胺衍生物:
其中:A为H、或与T一起形成一个键,T为-OH、
或与A一起形成一个键;
R代表H、C1-C6烷基、囟素、-NO2,当T与A形成一个键时,R也可以为
c)下式所示的秋兰姆衍生物:
其中:Y代表
R1代表C1-C4烷基,特别是二硫化四烷基秋兰姆、二乙基二硫代氨基甲酸锌。
d)下式所示的二苯基胍衍生物:
其中:R2代表H、C1-C6烷基,特别是R2为H或CH3的化合物。
另外,其它化合物,例如马来酐、二芳基甲脒以及二重氮基和三重氮基双环癸烯的衍生物也适于用作添加剂。
本发明的添加剂用量通常为每100重量份弹性体用0.1~3份(p.h.r),特别是0.2~2p.h.r。使用本发明的添加剂,除了可以明显地减少有毒产物溴化或碘化甲基或乙基产生(在某些情况下可减少90%)之外,还可赋予固化组合物下列特性:
-产生早期硫化所必须的时间(早期硫化时间)加长,因此,有较高的加工可靠性;
-混合物的门尼粘度下降,从而改进了加工性;
-对在180℃下交联速率和产率有适中的影响。
前述所有添加剂可用技术文献所述的已知方法制备。
适用于本发明的氟弹性体是那些含有作为固位化点的溴或碘原子的氟弹性体。
在这些众所周知的化合物中,应提及的有:偏氟乙烯与全氟丙烯同时也可与四氟乙烯与全氟乙烯醚的共聚物,该共聚物含有少量溴或碘,溴或碘可由少量溴化的或碘化的单体,如溴化烯烃、全氟溴烷基-全氟乙烯醚的聚合而引入,或者也可通过使用溴或碘烷基化合物链转移剂来引入。
基于用加有本发明添加剂的过氧化物固化的氟弹性体的混合物除了含有有机过氧化物外还含有其它常用组分,如碳黑和其它增强填料、过氧化物固化助剂(例如异氰尿酸三烯丙基酯)、金属氧化物或金属氢氧化物(例如PbO、ZnO)以及各种加工助剂。
下列实例仅仅用来说明本发明,而不限制本发明。
在固化条件下溴甲烷逸出的测定通常按下列方法进行。溴甲烷逸出的剂量装置:
在密闭反应器中,180℃温度、氮气氛和绝对压力为0.5kg/cm2下将20g微粒状混合物(聚合物+填料)处理30分钟。
然后,将混合物冷却至40~50℃,加入1毫升A114(C2Cl2F4,沸点为4℃)作为内标物。
进行气相混合,并用气相色谱分析。
柱:POROPAK Q
T=100℃
相反,在例2中,在通过测定从固化模上方收集的空气样品中的溴甲烷来测定在实际固化条下于170℃时所产生的实际逸出量。
所用的弹性体是:
P.1:由66.2%(摩尔)偏氟乙烯、18.2%全氟丙烯和15.2%四氟乙烯组成的含有溴化全氟乙基乙烯基醚(溴含量等于0.6%(重量))的三元共聚物。
P.2:由54.1%(摩尔)、22.2%全氟丙烯和22.9%四氟乙烯组成的含有溴化全氟乙基乙烯基醚(溴含量等于0.54%(重量))的三元共聚物。
混合物组份除了含有本发明的添加剂外,每100重量份共聚物中还含有下述组分:
-含有45% 2,5-二甲基-2,5-二叔丁基过氧化己烷的惰性填料(Luperco 101XL),3重量份;
-含有75%异氰尿酸三烯丙基酯(TAIC)的惰性填料,4重量份;
-PbO,3重量份。
按美国标准ASTM D2084/81用振动圆盘流变仪(ODR,孟山都型号)测定扭矩差值△(MH-ML),用以评估固化程度。
在180℃加热12分钟后用“arc3”测定最大扭矩MH。
实例1
用三元共聚物P.1进行试验。
未加本发明的固化添加剂的弹性体固化后扭矩△值等于71。
在某些试验中,溴甲烷逸出量降低得少,这是由于添加剂用量不足所致。按上述所给出的用量范围,增加添加剂用量就可以提高效果(参见试验实例7和8)。
试验21是比较试验,该试验的产品溴甲烷逸出量大大降低,但是同时固化受到影响,或大大地降低了固化程度。
表1
△扭矩
添加剂 溴甲烷逸
试验 添加剂 加入量 MH-ML 出量减少%
序号 (PHR) (标准=71)
1
1.65 60 72%
4
1.80 68 34%
表1(续)
△扭矩
添加剂 溴甲烷逸
试验 添加剂 加入量 MH-ML 出量减少%
序号 (PHR) (标准=71)
9
1.68 51 77%
表1(续)
△扭矩
添加剂 溴甲烷逸
试验 添加剂 加入量 MH-ML 出量减少%
序号 (PHR) (标准=71)
11
1.0 60 51%
14
0.5 65 28%
表1(续)
△扭矩
添加剂 溴甲烷逸
试验 添加剂 加入量 MH-ML 出量减少%
序号 (PHR) (标准=71)
二硫化四乙基秋兰姆
18
0.5 67 87%
二硫代二乙基氨基甲酸锌
巯基苯并噻唑锌盐
表1(续)
PHR △扭矩
添加剂 溴甲烷逸
试验 添加剂 加入量 MH-ML 出量减少%
序号 (PHR) (标准=71)
20
0.5 80 79%
吗啉二苯并噻唑硫酰胺
对比试验
对苯醌二肟
实例2
本试验的目的是为了检验例1所述的用实验室试验方法所测得的溴甲烷减少量与在实际条件下于170℃在模内固化过程中所能达到溴甲烷实际减少量之间的对应关系。实际减少量是通过分析从模中取出固化产物后立即收集到的模制品上方的空气样品来测定的。所用添加剂是二硫化巯基苯并噻唑(MBTS)。同时也进行未加添加剂的实验以便比较扭矩△及溴甲烷逸出量等数值。
本试验所用的弹性体是前述的P.2三元共聚物。
试验结果为分析测定的5个空气品样的平均值。
表2
添加剂 加入量 扭矩△ 溴甲烷逸出量减少% 溴甲烷逸出量减少%
PHR MH-ML 实验室测试值 模制时测试值
- - 62 - -
MBTS 0.25 64 79 62
MBTS 0.5 66 85 98
实例3
固化混合物及固化产品的特性。
下表列出了与未加添加剂的产品相比较的产品特性。
特别是由表3可以看出含有本发明添加剂的混合物的早期硫化时间明显比较长,门尼早期硫化粘度(135℃时)降低,121℃时的门尼粘度降低。这些特性均说明该混合物的加工性较好。
表4列出了表征固化程度的某些特性。
表5列出了固化材料的特性。
实例4
表6所列试验结果表明溴甲烷选出量的减少及固化程度随所用聚合物的类型及溴含量的不同而改变。
表6中所有试验均采用下式所示的苯基马来二酰亚胺作为添加剂:
固化混合物的其它组分如下:
Luperco 3p.h.r.
TAIC 4p.h.r.
PbO 3p.h.r.
碳黑 30p.h.r.
表6
聚合物 添加剂用量 扭矩△ 溴甲烷逸出量减少%
P.H.R. MH-ML
P.1 - 71 -
P.2 1.5 76 15
P.41 - 62 -
P.41 1.5 55 29
P.2+P.41(+)(混合物) - 65 -
P.2+P.41(+)(混合物) 1.5 64 37
聚合物P.41含53.4%偏氟乙烯;23.9%四氟乙烯;22.7%全氟丙烯以及溴化乙烯基醚,溴含量为0.93%。(+)混合聚合物中溴含量为0.72%。
Claims (2)
2、按照权利要求1所述的氟弹体组合物,其特征在于每100重量份氟弹体添加剂用量为0.2-2重量份。
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IT22995A/88 | 1988-12-16 | ||
IT8822995A IT1228054B (it) | 1988-12-16 | 1988-12-16 | Additivi per la vulcanizzazione con perossidi di fluoroelastomeri contenenti bromo o iodio |
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CN1025434C true CN1025434C (zh) | 1994-07-13 |
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EP (1) | EP0373973B1 (zh) |
JP (1) | JP2807005B2 (zh) |
CN (1) | CN1025434C (zh) |
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IT1255853B (it) * | 1992-10-12 | 1995-11-17 | Ausimont Spa | Composizioni di polimeri elastomerici vulcanizzabili per via ionica |
JP3082626B2 (ja) * | 1995-07-19 | 2000-08-28 | 日本メクトロン株式会社 | 含フッ素エラストマー組成物 |
IT1302986B1 (it) * | 1997-02-11 | 2000-10-18 | Ausimont Spa | Blends di elastomeri fluorurati e acrilici |
US6239223B1 (en) | 1997-09-05 | 2001-05-29 | Chemfab Corporation | Fluoropolymeric composition |
FR2771097B1 (fr) * | 1997-11-19 | 2000-01-14 | Atochem Elf Sa | Compositions a base de resine fluoree et de compose imide leur procede de preparation et leurs utilisations |
US8338542B1 (en) * | 2012-06-25 | 2012-12-25 | E I Du Pont De Nemours And Company | Curable fluoroelastomer composition |
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US2955104A (en) * | 1958-09-17 | 1960-10-04 | Du Pont | Process for curing fluoroelastomers |
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AU494969B2 (en) * | 1975-10-01 | 1978-04-13 | Ifield Engineering Pty. Limited | Improvements in bent axis pumps and motors |
JPS53125491A (en) * | 1977-04-08 | 1978-11-01 | Daikin Ind Ltd | Fluorine-containing polymer easily curable and its curable composition |
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US4529759A (en) * | 1984-12-07 | 1985-07-16 | E. I. Du Pont De Nemours And Company | Peroxide-curable brominated or iodinated fluoroelastomer composition containing an N,N,N',N'-tetrasubstituted 1,8-diaminonaphthalene |
JPS62260807A (ja) * | 1986-05-07 | 1987-11-13 | Nippon Mektron Ltd | 含フッ素重合体の製造方法 |
JP2888303B2 (ja) * | 1989-07-31 | 1999-05-10 | 日本メクトロン株式会社 | 架橋性含フッ素エラストマー組成物 |
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US5399633A (en) | 1995-03-21 |
AU633289B2 (en) | 1993-01-28 |
RU2087497C1 (ru) | 1997-08-20 |
IT1228054B (it) | 1991-05-27 |
IT8822995A0 (it) | 1988-12-16 |
CA2005356C (en) | 1996-04-30 |
DE68919063D1 (de) | 1994-12-01 |
EP0373973A3 (en) | 1991-10-23 |
DE68919063T2 (de) | 1995-03-09 |
US5502115A (en) | 1996-03-26 |
AU4676489A (en) | 1990-06-21 |
ES2063148T3 (es) | 1995-01-01 |
EP0373973B1 (en) | 1994-10-26 |
JPH02214758A (ja) | 1990-08-27 |
EP0373973A2 (en) | 1990-06-20 |
CA2005356A1 (en) | 1990-06-16 |
JP2807005B2 (ja) | 1998-09-30 |
ATE113306T1 (de) | 1994-11-15 |
CN1043511A (zh) | 1990-07-04 |
ZA899527B (en) | 1990-10-31 |
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