CN108137918A - 用于温室棚膜中的高性能抗滴落剂 - Google Patents
用于温室棚膜中的高性能抗滴落剂 Download PDFInfo
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Abstract
公开了一种膜,其包含、组成为或基本上组成为:a)聚烯烃组分;b)添加剂,所述添加剂包含i)第一聚氧化乙烯/聚乙烯共聚物,其具有1到7范围内的HLB值以及选自由CH3CH2(CH2CH2)aCH2CH2(OCH2CH2)bOH和CH3CH2(CH2CH2)aCO(OCH2CH2)bOH组成的群组的结构其中a是9到25且b是1到10;以及ii)第二聚氧化乙烯/聚乙烯共聚物,其具有7到18范围内的HLB值以及选自由CH3CH2(CH2CH2)aCH2CH2(OCH2CH2)bOH和CH3CH2(CH2CH2)aCO(OCH2CH2)bOH组成的群组的结构其中a是9到25且b是1到10。所述膜用于温室应用。
Description
技术领域
本发明涉及聚烯烃膜。更具体地说,本发明涉及用于温室应用的聚烯烃膜。
背景技术
滴落是由于“封闭体”的内部气氛与外部气氛的温度差和界面处的局部冷却而通常发生的现象。农用膜所包围的温室内的气氛含有从土壤或从植物中蒸发的饱和水蒸汽,由于水表面张力非常高(约72mN/m)且通常由聚乙烯(PE)、乙烯-乙酸乙烯酯(EVA)或聚氯乙烯(PVC)制成的温室棚膜的表面能较低,因此水蒸汽逐滴凝结在冷膜的内表面上而产生水滴。膜上的水滴因不规则反射而大大减少了入射的阳光且落在植物上的液滴能引起农作物受到物理损伤。
因此,为了避免滴落,使用抗滴落处理以使得温室棚膜内表面具有亲水性或通过添加表面活性剂来减少水表面张力。两种方法均能够使水汽凝结的液滴在表面上扩散且排掉,从而确保阳光透射到温室中且减少对植物的物理损伤。
目前,市场上可获得的大部分抗滴落膜并有低分子量添加剂(例如非离子型表面活性剂,诸如脱水山梨糖醇酯、聚氧化乙烯酯、丙三醇酯和聚丙三醇酯),所述添加剂从块体膜基质迁移到塑料膜的表面。表面上的这些低分子量表面活性剂能溶解于水中且减少水表面张力,以致“改性的水”能够在膜上扩散。典型的抗滴落添加剂浓度在1到5重量%范围内。然而,这些市售表面活性剂添加剂中通常大部分对非极性聚乙烯膜基质不具有良好亲和力。这些添加剂能够快速地从膜中扩散且容易被凝结水从膜表面洗掉,导致抗滴落服务时间缩短和膜抗滴落性能在相对较短的时间内降低。
因此,期望服务时间较长的抗滴落添加剂。
发明内容
本发明的一个较宽方面是一种膜,其包含、组成为或基本上组成为:a)聚烯烃组分;b)添加剂,所述添加剂包含
i)第一聚氧化乙烯/聚乙烯共聚物,其具有1到7范围内的HLB值以及选自由CH3CH2(CH2CH2)aCH2CH2(OCH2CH2)bOH和CH3CH2(CH2CH2)aCO(OCH2CH2)bOH组成的群组的结构
其中a是9到25且b是1到10;以及ii)第二聚氧化乙烯/聚乙烯共聚物,其具有7到18范围内的HLB值以及选自由CH3CH2(CH2CH2)aCH2CH2(OCH2CH2)bOH和CH3CH2(CH2CH2)aCO(OCH2CH2)bOH组成的群组的结构
其中a是9到25且b是1到10。
具体实施方式
-组分(a)-聚烯烃组分
所述膜包含聚烯烃组分。聚烯烃实例包括(但不限于)单烯烃与二烯烃的聚合物,例如聚丙烯、聚异丁烯、聚丁-1-烯、聚-4-甲基戊-1-烯、聚异戊二烯或聚丁二烯,以及环烯烃的聚合物(如环戊烷或降冰片烯的聚合物)、聚乙烯(例如高密度聚乙烯(HDPE)、高密度和高分子量聚乙烯(HDPE-HMW)、高密度和超高分子量聚乙烯(HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)和线性低密度聚乙烯(LLDPE))。
可以使用上述聚烯烃的混合物,例如聚丙烯与聚异丁烯、聚丙烯与聚乙烯(例如PP/HDPE)的混合物,以及不同类型的聚乙烯的混合物(例如LDPE/HDPE)。
聚烯烃组分的其它实例包括单烯烃与二烯烃彼此间或与其它乙烯基单体的共聚物,例如乙烯/丙烯共聚物、LLDPE以及其与LDPE的混合物、丙烯/丁-1-烯共聚物、丙烯/异丁烯共聚物、乙烯/丁-1-烯共聚物、乙烯/己烷共聚物、乙烯/甲基戊烯共聚物、乙烯/庚烯共聚物、乙烯/辛烷共聚物、丙烯/丁二烯共聚物、异丁烯/异戊二烯共聚物、乙烯/甲基丙烯酸烷酯共聚物、乙烯/乙酸乙烯酯共聚物和其盐,以及乙烯与丙烯和二烯(如己二烯、二环戊二烯或亚乙基-降冰片烯)的三聚物;以及此类共聚物彼此间和与上述其它聚合物的混合物,如聚丙烯/乙烯-丙烯共聚物、LDPE/乙烯-乙酸乙烯酯共聚物(EVA)、LDPE/乙烯-丙烯酸共聚物(EAA)、LLDPE/EVA、LLDPE/EAA以及其混合物。
聚烯烃组分典型地按90到99重量%的范围存在于所述膜中。本文中包括且本文中公开了90与99重量%之间的任何和所有值,例如聚烯烃组分可以占所述膜的90、90.2、91、92、92.5、93、96或97重量%。
-组分(b)(i)-第一PEO/PE组分
添加剂典型地按1到5重量%的范围存在于所述膜中。本文中包括且本文中公开了1与5重量%之间的任何值,例如所述添加剂可以占所述膜的1、2、2.4、3、3.5、4或5重量%。
所述添加剂包含至少一种第一聚氧化乙烯/聚乙烯(PEO/PE)共聚物组分。此共聚物通常具有选自由以下组成的群组的结构:CH3CH2(CH2CH2)aCH2CH2(OCH2CH2)bOH和CH3CH2(CH2CH2)aCO(OCH2CH2)bOH,其中a是9到25且b是1到10。
所述共聚物的亲水亲油平衡(HLB)值是利用PEO含量计算。举例来说,不含PEO组分的聚合物的HLB值为零且PEO含量为20%的PEO/PE共聚物的HLB值为4。第一聚氧化乙烯/聚乙烯共聚物的HLB值通常在1到7范围内。本文中包括且本文中公开了1至7内的任何值,例如HLB值可以是1、2、3、4、5、6或7。
PEO/PE组分的实例包括(但不限于)获自Baker Hughes的Unithox。
第一PEO/PE共聚物通常按10重量%到90重量%的范围存在于添加剂中。本文中包括且本文中公开了10至90重量%内的任何和所有范围;例如第一PEO/PE共聚物存在于所述膜中的范围可以是33重量%到50重量%。
-组分(b)(ii)-第二PEO/PE共聚物(表面活性剂)
在各种实施例中,所述添加剂进一步包含含有PEO/PE共聚物的第二添加剂。此共聚物通常具有与第一添加剂相同的结构。
第二PEO/PE共聚物通常具有高于第一PEO/PE共聚物的环氧乙烷含量,从而赋予其更高的HLB值。第二聚氧化乙烯/聚乙烯共聚物的HLB值通常在7到18范围内。本文中包括且本文中公开了7与18之间的任何值,例如HLB值可以是7、8、9、10、11、12、13、14、15、16、17或18。较高环氧乙烷含量允许第二添加剂修改水表面张力。
第二PEO/PE共聚物通常按10重量%到90重量%的范围存在于添加剂中。本文中包括且本文中公开了10至90重量%内的任何和所有范围;例如第二PEO/PE共聚物能以50重量%到67重量%的范围存在于所述膜中。
任选组分
在一些实施例中,所述膜中可以存在抗氧化剂。抗氧化剂实例包括(但不限于)烷基化单酚、烷基化氢醌、羟基化硫代二苯基醚、亚烷基双酚,苯甲基化合物、酰胺基苯酚、b-(3,5-二叔丁基-4-羟基苯基)-丙酸与一元或多元醇的酯、b-(5-叔丁基-4-羟基-3-甲基苯基)-丙酸与一元或多元醇的酯,b-(3,5-二叔丁基-4-羟基苯基)-丙酸的酰胺,以及其组合。在一些实施例中,所述膜中可以存在紫外线稳定剂。uv稳定剂实例包括(但不限于)2-(2'-羟基苯基)-苯并三唑、2-羟基-二苯甲酮、被取代的苯甲酸的酯、丙烯酸酯、丙二酸酯、位阻胺、羟基苯基-均-三嗪,以及其组合。
组合物制备方法
本发明的多层膜优选按照所属领域中通常已知的吹塑膜方法形成,但是可以使用其它方法,如铸膜或层合。
实例
原材料和实验:
所有原材料展示于表1中。
表1:原材料信息
符号‘CXX-EOY’表示具有特定数目个碳原子和环氧乙烷重复单元的化合物。举例来说,化合物‘C32-EO4’具有32个碳原子和4个环氧乙烷重复单元。
膜制备方法:
1.混配
首先,使用高强度混合器将添加剂(包括抗滴落剂、防雾剂)与LDPE粉末混合。接着在27mm双螺杆挤出机上进行混配。LLDPE从一个馈送器中馈送且LDPE粉末连同所有其它添加剂一起从另一个馈送器中馈送。将温度设定在约180℃且螺杆速度是250rpm。熔融温度是约230℃且总输出是20kg/h。
2.吹塑膜
在冲模直径为50mm的单层吹塑膜生产线上制备膜。吹胀比(BUR)是约2.5。膜厚度是60um。
所有配方列于表2中。CE-1到CE-9是具有一种抗滴落组分的比较实例。CE-10是比较实例,其含有2种类型的抗滴落添加剂,但不含HLB值低于7的PEO/PE共聚物。CE-11是含有2种类型的抗滴落添加剂的比较实例。一种是疏水性C32-EO4(HLB=4)且另一种是不具有PEO/PE的市售抗滴落剂KF650。CE-12和CE-13是含有疏水性C32-EO4和疏水酯的比较实例,其膜中不含有PEO/PE。
IE-1到IE-10是含有2种或更多种类型的PEO/PE共聚物的本发明实例。一种类型的PEO/PE组分具有不良溶解性且HLB值是约4(例如C50-EO5或C32-EO4,以增强膜表面张力)。且存在其它类型的水溶性PEO/PE组分,其HLB值大于7(例如C32-EO10、C18-EO9),以降低水表面张力。
表2.抗滴落膜的配方和测试结果
膜加速抗滴落测试:
根据中国国家标准GB 4455-2006测试膜抗滴落性能。将膜夹持在水浴的笼子上以形成封闭空间且用冲压锥使膜产生15度倾斜角。将水浴中的水加热到60℃且水蒸汽凝结而在膜上形成薄水层。凝结水流回到水浴中且抗滴落剂通常将逐渐地被洗掉。膜的内表面上将形成不透明的水滴及/或透明的水片/流,导致抗滴落性能降低。
失效准则设定为:
1.不透明水滴面积大于总膜面积的30%。
2.水片/流的面积大于总膜面积的50%。
当抗滴落性能失效时,记录抗滴落服务时间(天数)。
结果:
所有膜样品的抗滴落性能展示于表2中。
比较实例:
比较实例CE-1到CE-9仅含有一种类型的抗滴落添加剂。基准抗滴落剂KF650(基于醇酯的抗滴落剂)之一的寿命当用PE基质配制时是12天(CE-7)且当用EVA基质配制时是15天(CE-8)。单组分PEO/PE抗滴落剂的寿命类似于KF 650(CE-2、CE-3和CE-4为13到15天)或比KF 650更差(CE-1、CE-5和CE6为2到6天)。另一种市售抗滴落剂LA-6的性能是14天。
CE-10含有2种类型的抗滴落添加剂,但不含有HLB值低于7的PEO/PE。膜寿命仅为14天。
CE-11含有2种类型的抗滴落添加剂。一种是疏水性C32-EO4(HLB=4)且另一种是KF650,但不含有PEO/PE。膜性能是14天。
CE-12和CE-13是含有疏水性C32-EO4和疏水酯的比较实例,其膜中不含有亲水性PEO/PE。这2个膜的抗滴落寿命非常短,仅持续几天。
本发明实例:
本发明实例含有若干类型的PEO/PE共聚物,其中至少一种组分的水溶性不良(HLB值为4的C50-EO5或C32-EO4),且至少一种水溶性PEO/PE组分具有大于7的HLB值。根据60℃下进行的加速测试,任一个本发明实例的寿命均长于20天,比单组分比较实例(CE-1到CE-9)和双组分比较实例(CE-10和CE-11)长得多。IE-2(C32-EO4/C32-EO10掺混物)和IE-4(C32-EO4/C18-EO4掺混物)的寿命长于40天,而IE-5和IE-6的寿命长于50天,比最佳比较实例的寿命长超过3倍。
Claims (6)
1.一种膜,包含:
a)聚烯烃组分;
b)添加剂,所述添加剂包含
i)第一聚氧化乙烯/聚乙烯共聚物,其具有1到7范围内的HLB值和选自由以下组成的群组的结构:CH3CH2(CH2CH2)aCH2CH2(OCH2CH2)bOH和CH3CH2(CH2CH2)aCO(OCH2CH2)bOH
其中a是9到25且b是1到10;以及
ii)第二聚氧化乙烯/聚乙烯共聚物,其具有7到18范围内的HLB值以及选自由CH3CH2(CH2CH2)aCH2CH2(OCH2CH2)bOH和CH3CH2(CH2CH2)aCO(OCH2CH2)bOH组成的群组的结构
其中a是9到25且b是1到10。
2.根据权利要求1所述的膜,其中所述聚烯烃组分选自由以下组成的群组:低密度聚乙烯、线性低密度聚乙烯以及其组合。
3.根据权利要求1所述的膜,其中所述添加剂按1重量%到5重量%范围内的量存在于所述膜中。
4.根据权利要求1所述的膜,其中所述第一聚氧化乙烯/聚乙烯共聚物按33重量%到50重量%的范围存在于所述添加剂中。
5.根据权利要求1所述的膜,其中所述第二聚氧化乙烯/聚乙烯共聚物按50重量%到67重量%的范围存在于所述添加剂中。
6.一种温室棚膜,其由根据权利要求1所述的膜制备。
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WO2017045198A1 (en) | 2017-03-23 |
US20180230280A1 (en) | 2018-08-16 |
EP3350264A4 (en) | 2019-03-13 |
ES2890148T3 (es) | 2022-01-17 |
US10723851B2 (en) | 2020-07-28 |
MY184302A (en) | 2021-03-31 |
BR112018004213A2 (pt) | 2018-09-25 |
JP2018529006A (ja) | 2018-10-04 |
EP3350264B1 (en) | 2021-08-04 |
EP3350264A1 (en) | 2018-07-25 |
MX2018003064A (es) | 2018-05-07 |
CN108137918B (zh) | 2020-12-01 |
CA2998400A1 (en) | 2017-03-23 |
AR106023A1 (es) | 2017-12-06 |
BR112018004213B1 (pt) | 2022-04-19 |
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