CN106795296B - 用于厌氧产品的组合体 - Google Patents
用于厌氧产品的组合体 Download PDFInfo
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- CN106795296B CN106795296B CN201480081041.6A CN201480081041A CN106795296B CN 106795296 B CN106795296 B CN 106795296B CN 201480081041 A CN201480081041 A CN 201480081041A CN 106795296 B CN106795296 B CN 106795296B
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- container body
- container
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- polyethylene
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- 239000000203 mixture Substances 0.000 claims abstract description 59
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- 239000004628 starch-based polymer Substances 0.000 claims abstract description 29
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- 239000000463 material Substances 0.000 claims abstract description 24
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
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- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 4
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- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
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- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Images
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Abstract
本发明涉及一种组合体,其包括:容器,所述容器具有容器主体,所述容器主体能够被氧气充分地透过以防止其中所容纳的可厌氧固化组合物由于缺氧而发生固化;以及容纳于所述容器中的可厌氧固化组合物。所述容器主体由塑性材料构造,所述塑性材料由热塑性淀粉组分与聚乙烯的共混物形成。
Description
技术领域
本发明涉及一种用于厌氧产品(例如厌氧密封剂和粘合剂)的组合体(pack)。特别受关注的是液态厌氧产品。厌氧产品在缺乏氧气(空气)的情况下固化、凝结(set-up)或聚合。
背景技术
本文使用的术语厌氧用以指在缺乏空气的情况下固化、凝结或聚合的配制物。包括丙烯酸类体系,所述体系包括基于丙烯酸酯和甲基丙烯酸酯的组合物。这包括结构厌氧材料。
应用包括那些需要拉伸粘合强度;扭转粘合强度(例如螺纹紧锁配制物)等的。
已经生产了许多类型用于厌氧产品的容器。这些容器包括瓶子、盒中袋容器等。
包装厌氧粘合剂的一个关键考虑因素是贮存稳定性。如果没有存在足够的氧气透过组合物的块(mass)以防止发生固化,贮存稳定性会受损。通常这意味着不是所有的材料都适合用于制备容纳可厌氧固化产品的容器。
此外,还可能会有相容性问题。例如,可厌氧固化组合物的组分和容器主体材料的组分可能彼此不相容。例如,一些材料可能会对可厌氧固化组合物的化学特性和/或物理特性产生不利影响。
因此,总是需要用于制备容纳可厌氧固化产品的容器的替代材料。
特别是,需要表现出合适的贮存稳定性的包括容器和其中所容纳的可厌氧固化产品的替代组合体。
发明内容
在一个方面中,本发明提供这样一种组合体,其包括:
(i)容器,所述容器具有容器主体,所述容器主体能够被氧气充分地透过以防止其中所容纳的可厌氧固化组合物由于缺氧而发生固化;和
(ii)容纳在所述容器中的可厌氧固化组合物;
其中所述容器主体由塑性材料构造,所述塑性材料由热塑性淀粉组分与聚乙烯的共混物形成。
作为形成容器主体的替代材料这是想要的。它具有所想要的特性。而且,热塑性淀粉组分中使用的淀粉可以来自可再生资源。
已发现该材料与各种各样可厌氧固化材料配制物相容。
该材料显示出对于贮存可厌氧固化产品而言想要的特性。特别是,已发现形成容器主体的材料的性能与较多常规材料的性能相当。
此外,该材料是多方面适用的。例如,它可以是足够硬的以形成瓶子形式的容器。可以形成容器主体的可挤压形式。例如,容器主体可以是可挤压容器形式,所述可挤压容器任选地配有分配装置,例如分配喷嘴。例如,可以提供一种包括盖和喷嘴的分配组件。
已发现本发明的组合体显示出良好的贮存稳定特性,这使得其适合于制造不同类型的容器。
另外,可以使用各种各样的材料共混物。
例如,热塑性淀粉组分中的淀粉可以以用于形成容器主体的共混物的6重量%至33重量%的量存在。
热塑性淀粉组分中的淀粉可以以用于形成容器主体的共混物的13重量%至32重量%的量存在。任选地,热塑性淀粉以用于形成容器主体的共混物的20重量%至30重量%的量存在。例如,热塑性淀粉组分中的淀粉可以以用于形成容器主体的共混物的23重量%至30重量%的量存在。
热塑性淀粉组分中的淀粉可以以用于形成容器主体的共混物的约26重量%的量存在。
热塑性淀粉组分中的淀粉可以以热塑性淀粉组分的形式使用。也就是说,淀粉可以与一种或多种其它材料共同使用。例如,热塑性淀粉组分可以是与增塑剂共混的淀粉。这可能是为了使该淀粉更容易共混而所想要的。例如,想要的是热塑性淀粉组分可与非淀粉材料例如(热)塑性材料共混。想要的是,淀粉来自天然来源。
可以使用任何合适的增塑剂。例如,可以使用多官能醇或多官能醇的组合。合适的多官能醇包括甘油和山梨醇及它们的组合。
在热塑性淀粉组分中还可以使用相容剂以使淀粉组分与待与其共混的聚合物相容。例如,所使用的相容剂可使热塑性淀粉组分与聚乙烯相容。例如,相容剂可以是具有与淀粉相容的基团和跟与其共混的热塑性材料相容的基团的聚合物。想要的是这样一种共聚物,其中一种单体在性质上类似于待与之相容的聚合物(其与淀粉相容),并且其中经共聚的共聚单体与淀粉相容,例如对淀粉具有反应活性,如对淀粉的羟基具有反应活性。在这方面,可以使用接枝或无规共聚物,其中聚合物主链是与聚合物相容的单体并且共聚单体作为侧基连接在主链上。
对于本发明,想要的是具有与聚乙烯相容的主链的任何相容剂。例如,主链可以是聚乙烯主链。可以使用任何合适的侧基共聚单体。可以使用羧酸、羧酸酐和丙烯酸的酯作为共聚单体。本发明中一种合适的相容剂是聚乙烯-共-丙烯酸。
为了便于共混,可以将淀粉和任选存在的增塑剂与一定量的待稍后共混的聚合物预混。例如,可以将热塑性淀粉组分与聚乙烯共混。
国际专利申请WO2011/020170中描述和请求保护的方法适合于制备本发明的热塑性淀粉。
在使用中使用除包含淀粉组分之外还包含其它组分的热塑性淀粉组分的情况下,本文给出的关于淀粉量的值仅指淀粉,并不包括所述其它组分。
例如,聚乙烯可以以用于形成容器主体的共混物的66重量%至94重量%的量存在。任选地,聚乙烯以用于形成容器主体的共混物的67重量%至87重量%的量存在。聚乙烯可以以用于形成容器主体的共混物的70重量%至80重量%的量存在。例如,聚乙烯可以以用于形成容器主体的共混物的约74重量%的量存在。
在热塑性淀粉组分中使用聚乙烯的情况下,本文给出的关于聚乙烯量的值指容器中所存在的聚乙烯的总量。(为避免存疑,该量不包括任何可能存在的聚乙烯的共聚物,例如作为相容剂存在的聚乙烯的共聚物)。
容器主体的氧气透过率是基于4mm壁厚24小时内至少2.4cm3。
本发明的组合体可以容纳在一个良好粘度范围内的材料。例如,可厌氧固化组合物的粘度可以为约10厘泊至约8000厘泊。
合适地,聚乙烯为基于LDPE的材料。
如果需要,形成容器主体的共混物可以包含增塑剂。
如上所述,对于一些最终用途应用,想要的是,容器主体是可挤压的,从而用于分配可厌氧固化组合物。例如,可以采用可挤压瓶的形式。
容器可还包括分配喷嘴,任选地构成用于容器主体的封盖(closure)的一部分,用于从容器中分配厌氧产品。
容器可还包括用于从容器中分配厌氧产品的分配封盖。所述封盖可包括喷嘴。
容器主体可被颜料着色。例如,可以将颜料与形成容器主体的组分共混。这可以在不损害其中所容纳的产品的贮存稳定性的情况下完成。
可厌氧固化材料可包含选自(甲基)丙烯酸酯、硫醇烯(thiolene)、硅氧烷、乙烯基(vinyl)以及——当然——它们的组合的单体。
可厌氧固化单体可以是(甲基)丙烯酸酯单体。适合于在可厌氧固化组合物中作为(甲基)丙烯酸酯组分使用的(甲基)丙烯酸酯单体可以选自各种各样的材料,例如H2C=CGCO2R1代表的这些,其中G可以是氢、卤素或具有1至约4个碳原子的烷基,R1可以选自具有1至约16个碳原子的烷基、环烷基、烯基、环烯基、烷芳基、芳烷基或芳基,所述基团中的任何一个视情况而定可任选地被硅烷、硅、氧、卤素、羰基、羟基、酯、羧酸、脲、氨基甲酸酯、碳酸酯、胺、酰胺、硫、磺酸酯、砜等取代或间断。
适合用于本发明组合体中的另外的(甲基)丙烯酸酯单体包括多官能(甲基)丙烯酸酯单体,例如但不限于:二官能或三官能(甲基)丙烯酸酯,如聚乙二醇二(甲基)丙烯酸酯,四氢呋喃(甲基)丙烯酸酯和二(甲基)丙烯酸酯,(甲基)丙烯酸羟丙酯(“HPMA”),己二醇二(甲基)丙烯酸酯,三羟甲基丙烷三(甲基)丙烯酸酯(“TMPTMA”),二甘醇二甲基丙烯酸酯,三甘醇二甲基丙烯酸酯(“TRIEGMA”),四甘醇二甲基丙烯酸酯,二丙二醇二甲基丙烯酸酯,二(戊二醇)二甲基丙烯酸酯,四甘醇二丙烯酸酯(tetraethylene diglycol diacrylate),双甘油四甲基丙烯酸酯,四亚甲基二甲基丙烯酸酯,二甲基丙烯酸亚乙基酯,新戊二醇二丙烯酸酯,三羟甲基丙烷三丙烯酸酯以及双酚A单(甲基)丙烯酸酯和双酚A二(甲基)丙烯酸酯,如乙氧基化双酚A(甲基)丙烯酸酯(“EBIPMA”),和双酚F单(甲基)丙烯酸酯和双酚F二(甲基)丙烯酸酯,如乙氧基化双酚F(甲基)丙烯酸酯。
可用于本文中的其它(甲基)丙烯酸酯单体还包括有机硅(甲基)丙烯酸酯部分(“SiMA”),例如在美国专利号5,605,999(Chu)中教导和要求保护的那些,所述专利的公开内容通过援引加入的方式明确纳入本申请中。
当然,也可使用单体的组合,例如(甲基)丙烯酸酯单体的组合。
基于组合物的总重量,(甲基)丙烯酸酯组分应构成组合物的约10至约90重量%,例如约60至约90重量%。
附图说明
仅以举例的方式并结合附图描述本发明的实施方案,其中:
图1为在下文实验中制备并测试的50ml(红色)着色瓶子的图像;
图2为示出对瓶子(例如图1中所示的瓶子)如下所述进行的柔韧性测试的结果的曲线图。
具体实施方式
图1示出了在下文实验中制备并测试的50ml(红色)着色瓶子的图像(照片)。图像中包括直尺以提供刻度指示。(如下所述制备类似的瓶子以容纳250ml产品。)
使用聚乙烯与热塑性淀粉的共混物以形成容器主体。随后通过使用该容器主体和用于容器的封盖形成组合体。特别是,将可厌氧固化粘合剂放置于该容器中。已发现该容器表现出与由PE单独形成的相当的容器相当的贮存稳定性。
以下论述了组合体的制造、所进行的测试以及那些测试的结果:
实验
可厌氧固化粘合剂位于其中的呈瓶形式的组合体以通常被称为“最小”产品填充体积出售——所述容器没有被填充至顶部,而是在容器中留下相当大的顶部空间。例如,组合体分别具有50ml和250ml厌氧产品的填充物出售,即使容器本身具有大得多的容量,例如分别具有约106ml和445ml的内部容积。需要额外的顶部空间以通过接触氧气来保持产品稳定。
由100%LDPE制备的和由60%相同的LDPE与40%Cardia BLF02(Cardia BL-F02是市售可得的热塑性淀粉与聚乙烯的共混物——可获自Cardia Bioplastics Unit 18/35Dunlop Road Mulgrave,Victoria 3170,澳大利亚)组成的替代物制备的两种尺寸的现存瓶子中放置有50ml或250ml产品。进行规定试验的产品是下表1中指明的产品270、243、242、278、290、542、549、601、638、648、649、2700、2400和6300。
Cardia BL-F02是包含淀粉的热塑性淀粉材料、甘油、山梨醇、聚乙烯-共-丙烯酸和聚乙烯。Cardia BL-F02约为(以重量计):66%淀粉,30%聚乙烯,以及剩下4%的甘油、山梨醇和聚乙烯-共-丙烯酸。
在填充后将瓶子用封盖密封。
瓶子通过在双头挤出吹塑机上的双腔模具制备。使用40%Cardia BLF02制备的瓶子具有以下尺寸并且其内部放置有50ml厌氧产品:
50ml
使用40%Cardia BLF02制备的瓶子具有以下尺寸并且其内部放置有250ml厌氧产品:
250ml
然后对经填充的样品进行如下加速(35℃和45℃/98%相对湿度)老化试验程序和实时(22℃——通常一般被称为室温,RT)老化试验程序:
4周@45℃/98%RH
8周@35℃
16周@35℃
6个月@22℃
12个月@22℃
18个月@22℃
24个月@22℃
在22℃下实时老化的时间长度取决于产品的贮存期,大多数情况下所述贮存期为24个月。
产品和它们的具体测试点列于下面表1中。(在提交本申请时,18和24个月的测试仍在进行,但到目前为止性能与常规LDPE瓶子相似。)产品和其测试结果列于下面表2中。与LDPE瓶相当的性能结果被认为是正面结果。
一旦完成测试点,就检查两组瓶子,目测比较以获得产品胶凝和/或包装劣化的任何证据以及/或者泄漏的证据。
随后测试样品以确保满足了所需性能。为此使用标准测试方法STM-754、STM-8、STM-701和STM-734。
对未填充的瓶子进行与LDPE和HDPE对比的柔韧性测试和氧气透过率测定。也对它们进行了尺寸测量以确保每个瓶在表格尺寸所示的规格内。
氧气透过试验(OTR)按照ASTMF1307-02使用具有电量传感器(coulometricsensor)的Mocon Oxtran 2/21设备测定。安装瓶子,用氮气流吹扫其内部12小时,同时将其外部暴露于23℃、50%RH的空气(20.8%氧气)中。采用收敛模式(converge mode)测试瓶子。当电流传输速率小于该电流传输速率之前5个周期(30分钟/周期)所获得的传输速率之间差值的1%时,平衡建立。
结果是针对100%氧气而言的。对每种瓶类型测试四个样品。在测试之前使用AiLeakmeter 120电子捕获气体检测器检查所安装瓶的完整性。结果如下。
Purell是可获自Lyondell Bassell,Houston,Texas,USA的产品的商品名。
Marlex是可获自Phillips Chemical International N.V.,Overijse,Belgium的产品的商品名。
在使用P/2N不锈钢探针的TA-XT2i稳定微系统质构仪(Stable MicrosystemsTexture Analyser)上测定瓶子的柔韧性。将测试速度设定为0.5mm分钟并且将与中心位置的距离设定为6.5mm。将瓶子平放于在水平位置的板上,探针以垂直方向朝下。将连接的探针设置在起始位置,该位置没有施加到瓶壁的面的负载。单元以测试速度运行,直到达到目标距离,并且产生输出值(力/kg)对距离的曲线图以比较柔韧性。每个瓶类型测定三个样品。
对50ml瓶进行这种测试的结果列于图2中。假定250ml瓶具有相当的氧气透过性。
表1
产品 | 测试点 |
Loctite 270 | 全部测试点 |
Loctite 243 | 全部测试点 |
Loctite 242 | 仅6和12个月@22℃ |
Loctite 278 | 仅6和12个月@22℃ |
Loctite 290 | 除了6个月@22℃之外全部测试点 |
Loctite 542 | 仅6和12个月@22℃ |
Loctite 549 | 没有4周@45℃/98%RH.贮存期12个月@22℃ |
Loctite 601 | 全部测试点 |
Loctite 638 | 除了4周@45℃/98%RH之外全部测试点 |
Loctite 648 | 除了4周@45℃/98%RH之外全部测试点 |
Loctite 649 | 至12个月@22℃(贮存期)的全部测试点 |
Loctite 2700 | 至18个月@22℃(贮存期)的全部测试点 |
Loctite 2400 | 至18个月@22℃(贮存期)的全部测试点 |
Loctite 6300 | 至12个月@22℃(贮存期)的全部测试点 |
结论
根据上述实验制备的瓶子清楚地示出了,本发明的组合体提供了与现有组合体(例如LDPE)相当的整体稳定性。此外,瓶子显示与其中的内容物相容。没有出现容器中的产品过早固化/胶凝的问题。而且,该容器稍微更容易挤压。这在具有不同组成的各种各样的产品中均有体现。
总体来说,在产品稳定性和相容性、性能、氧气透过性方面,由热塑性淀粉与LDPE的共混形成的瓶子提供了与相当的100%LDPE瓶子相同的性能,并且其稍微更易挤压。
当本文中结合本发明使用词语“包括/包含(comprise/comprising)”和词语“具有/包括(having/including)”时,其用于指明存在所述特征、整数、步骤或组分但不排除存在或添加一种或多种其它特征、整数、步骤、组分或其组。
应当理解的是,为了清楚起见在单独的实施方案中描述的本发明的某些特征也可以组合提供在单个实施方案中。相反地,为了简洁起见在单个实施方案中描述的本发明的各种特征也可以单独提供或以任何合适的子组合提供。
Claims (20)
1.组合体,包括:
a.容器,所述容器具有容器主体,所述容器主体能够被氧气充分地透过以防止其中所容纳的可厌氧固化组合物由于缺氧而发生固化;和
b.容纳于所述容器中的可厌氧固化组合物;
其中所述容器主体由塑性材料构造,所述塑性材料由热塑性淀粉组分与聚乙烯的共混物形成。
2.根据权利要求1所述的组合体,其中所述热塑性淀粉组分中的淀粉来自于可再生资源。
3.根据权利要求1或2所述的组合体,其中所述热塑性淀粉组分中的淀粉以所述用于形成容器主体的共混物的6重量%至33重量%的量存在。
4.根据权利要求1或2所述的组合体,其中所述热塑性淀粉组分中的淀粉以所述用于形成容器主体的共混物的13重量%至32重量%的量存在。
5.根据权利要求1或2所述的组合体,其中所述热塑性淀粉组分中的淀粉以所述用于形成容器主体的共混物的20重量%至30重量%的量存在。
6.根据权利要求1或2所述的组合体,其中所述热塑性淀粉组分中的淀粉以所述用于形成容器主体的共混物的23重量%至30重量%的量存在。
7.根据权利要求1或2所述的组合体,其中所述热塑性淀粉组分中的淀粉以所述用于形成容器主体的共混物的26重量%的量存在。
8.根据权利要求1或2所述的组合体,其中所述聚乙烯以所述用于形成容器主体的共混物的66重量%至94重量%的量存在。
9.根据权利要求1或2所述的组合体,其中所述聚乙烯以所述用于形成容器主体的共混物的67重量%至87重量%的量存在。
10.根据权利要求1或2所述的组合体,其中所述聚乙烯以所述用于形成容器主体的共混物的70重量%至80重量%的量存在。
11.根据权利要求1或2所述的组合体,其中所述聚乙烯以所述用于形成容器主体的共混物的74重量%的量存在。
12.根据权利要求1或2所述的组合体,其中所述容器主体的氧气透过率是基于4mm壁厚24小时内至少2.4cm3。
13.根据权利要求1或2所述的组合体,其中所述可厌氧固化组合物的粘度是10厘泊至8000厘泊。
14.根据权利要求1或2所述的组合体,其中所述聚乙烯是LDPE。
15.根据权利要求1或2所述的组合体,其中所述形成容器主体的共混物包含增塑剂。
16.根据权利要求1或2所述的组合体,其中所述容器主体是可挤压的,从而用于分配所述可厌氧固化组合物。
17.根据权利要求1或2所述的组合体,其中所述容器主体是瓶子。
18.根据权利要求1或2所述的组合体,其中所述容器还包括分配喷嘴,任选地构成所述容器主体的封盖的一部分,从而用于从所述容器中分配厌氧产品。
19.根据权利要求1或2所述的组合体,其中所述容器还包括分配封盖,从而用于从所述容器中分配厌氧产品。
20.根据权利要求1或2所述的组合体,其中所述容器主体被颜料着色。
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CN (1) | CN106795296B (zh) |
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EP3177674B1 (en) | 2019-10-02 |
RU2678268C2 (ru) | 2019-01-24 |
BR112017002287B1 (pt) | 2021-07-27 |
MX378250B (es) | 2025-03-10 |
EP3177674A1 (en) | 2017-06-14 |
BR112017002287A2 (pt) | 2017-11-21 |
KR20170039241A (ko) | 2017-04-10 |
KR20190110626A (ko) | 2019-09-30 |
CN106795296A (zh) | 2017-05-31 |
US20170145196A1 (en) | 2017-05-25 |
AU2014402919A1 (en) | 2017-03-02 |
RU2017107024A (ru) | 2018-09-07 |
CA2957325A1 (en) | 2016-02-11 |
MX2017001576A (es) | 2017-05-10 |
JP6702940B2 (ja) | 2020-06-03 |
JP2017529285A (ja) | 2017-10-05 |
AU2014402919B2 (en) | 2019-05-02 |
WO2016019998A1 (en) | 2016-02-11 |
KR102197217B1 (ko) | 2021-01-05 |
RU2017107024A3 (zh) | 2018-09-07 |
US10189977B2 (en) | 2019-01-29 |
CA2957325C (en) | 2020-07-14 |
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