CN114381034A - 一种农用聚烯烃薄制品高性能耐候复配物及其制备方法 - Google Patents
一种农用聚烯烃薄制品高性能耐候复配物及其制备方法 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 44
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004611 light stabiliser Substances 0.000 claims abstract description 39
- 150000001412 amines Chemical class 0.000 claims abstract description 30
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 15
- 230000002745 absorbent Effects 0.000 claims abstract description 11
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- 239000000203 mixture Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- -1 2- (2' -hydroxyphenyl) -1,3, 5-triazine compound Chemical class 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 7
- 235000013539 calcium stearate Nutrition 0.000 claims description 7
- 239000008116 calcium stearate Substances 0.000 claims description 7
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种农用聚烯烃薄制品高性能耐候复配物,按质量百分比,所述复配物包括如下组分:受阻胺光稳定剂50~80%;三嗪类紫外线吸收剂5~20%;无机防晒剂5~20%,吸酸剂5~10%;本发明提供的复配物添加到农用聚烯烃薄制品后,能够大幅增强受阻胺光稳定剂与紫外线吸收剂的协同耐候作用,降低酸性物质对耐候助剂的对冲作用,因此可大幅延长农用聚烯烃薄制品在苛刻环境下的使用年限;本发明还公开了该复配物具体制备方法。
Description
技术领域
本发明涉及高分子材料领域,具体地涉及一种农用聚烯烃薄制品高性能耐候复配物及其制备方法。
背景技术
聚烯烃树脂包括聚乙烯(PE),聚丙烯(PP)等,其广泛应用于棚膜,地膜,防草布,集装袋,土工无纺布等户外制品中。聚烯烃树脂的薄弱键(如主链上的叔碳原子),在高能紫外线的照射和氧气作用下,易被氧化产生较多的活性自由基,并进入恶性自动催化氧化的循环过程中,导致分子链的断裂,制品力学性能丧失,使用寿命大幅下降。
改善树脂耐候稳定性最为行之有效的方式是添加光稳定剂,主流的光稳定剂有受阻胺光稳定剂和紫外线吸收剂两大类。两者都是在20世纪六七十年代发明的,其中受阻胺光稳定剂能够多渠道的捕捉树脂体系中的自由基,并能循环再生,其高效且持久的耐候效果成为聚烯烃制品主要的耐候助剂。
为了最大程度地延长聚烯烃制品在户外的使用寿命,科学工作者们进行诸多研究,发现不同光稳定剂之间具有良好的协效作用。Kurumada T在《Synergism of hinderedamine light stabilizers and UV-absorbers》中研究了常规户外条件下,受阻胺光稳定剂与紫外线吸收剂存在的最佳协效比例,其中聚烯烃树脂中两者最佳配比为3:1-4:1。EP1500675A1中提到使用数均分子量大于500的受阻胺光稳定剂与三嗪类紫外线吸收剂在挤出或模塑制品中能够起到很好的耐候作用。
受阻胺光稳定剂和紫外线吸收剂的协效作用同制品厚度及使用环境都有着密切关系。一方面,极性耐候助剂与非极性的聚烯烃树脂相容性不够,尤其低分子量的紫外线吸收剂易在薄制品中向表面析出;另一方面,紫外线吸收剂效能与制品的厚度成正比(朗伯-比尔定律),当制品厚度低于100um时,紫外线吸收剂的耐候防护效果相对较差。此外,苛刻的使用环境也会影响两者协效作用的发挥,例如农用棚膜,其长期处于硫磺熏蒸,大量杀虫剂的喷洒环境中,这些酸性化合物会逐渐渗透到PE棚膜中,与碱性的受阻胺光稳定剂发生成盐反应,使之受阻胺光稳定剂在发挥耐候作用之前失效。
因此,有必要开发农用聚烯烃薄制品的新型的光稳定剂复配体系,满足相关制品在农用领域的适用性及耐久性。
发明内容
为解决上现有技术中耐候体系不足的问题,本发明提供了一种农用聚烯烃薄制品高性能耐候复配物及其制备方法,使得酸性环境下的农用聚烯烃薄制品具有优异的耐候性。
为达到上述目的,本发明的技术方案如下:
本发明提供一种农用聚烯烃薄制品高性能耐候复配物,按质量百分比包括受阻胺光稳定剂50~80%、三嗪类紫外线吸收剂5~20%,无机防晒剂5~20%、吸酸剂5~10%。
进一步地,所述受阻胺光稳定剂的数均分子量大于2000。
进一步地,所述受阻胺光稳定剂为HALS 944、HALS 3346、HALS 3529、HALS 119、HALS 2020、HALS 622中的一种或两种。
进一步地,所述三嗪类紫外线吸收剂为2-(2‘-羟苯基)-1,3,5-三嗪化合物。
进一步地,所述三嗪类紫外线吸收剂为UV 1577、UV 1164、UV 1600、UV 400中的一种。
进一步地,所述无机防晒剂的粒径为10~200nm;优选为30~80nm。
进一步地,所述无机防晒剂为氧化铈、氧化钛、氧化锌、蒙脱土、累托石中的一种。
进一步地,所述吸酸剂为碱性金属氧化物、叔胺类有机物、硬脂酸盐化合物中的一种。
进一步地,所述吸酸剂为氧化钙、氧化镁、水滑石、硬脂酸钙、硬脂酸锌、三正十二胺中的一种。
本发明还提供一种农用聚烯烃薄制品高性能耐候复配物的制备方法,包括以下步骤:
S1:将受阻胺光稳定剂、三嗪类紫外线吸收剂、无机防晒剂、吸酸剂在高速混合机中混合,转速为800-1000rpm,时长为2-5min;
S2:将S1所得混合物喂入预混造粒机,工艺温度设置为80~130℃,螺杆长径比为25-40,采用热环切加风冷冷却工艺,制得农用聚烯烃薄制品高性能耐候复配物。
本发明的有益效果为:
本发明提供的农用聚烯烃薄制品高性能耐候复配物,利用了不同光稳定剂之间的协效作用,使其对聚烯烃树脂具有良好的耐候防护效果。该复配物能够在制品的厚度低于100um,高酸性环境等条件下,仍发挥良好的耐候效果,并不会影响透明制品的透光率,突破了传统受阻胺光稳定剂与紫外线吸收剂之间复配的应用局限性。其次,该高性能耐候复配物物料成本较低,生产工艺相对简单,可在农用聚烯烃薄制品大范围推广使用,具有良好的市场应用价值。
具体实施方式
下面结合具体实施方式,进一步阐明本发明,应理解下述具体实施方式仅用于说明本发明而不用于限制本发明的范围。
实施例1
称量1kg受阻胺光稳定剂HALS 119,0.4kg的三嗪类紫外线吸收剂UV 1577,0.4kg的粒径为30~50nm的纳米氧化锌和0.2kg的硬脂酸钙,将之加入高混机中800rpm混合5min。混合均匀的物料加入到预混造粒机,挤出机温控设置为120℃,螺杆长径比为30:1,采用热环切加风冷冷却工艺,得到该配方的高性能耐候复配物。
将100g高性能耐候复配物,20g抗氧剂B215和880gLLDPE树脂混合均匀,然后经过双螺杆挤出机加工并冷却成型,得到耐候母粒(A-1)。
实施例2
称量1.4kg的受阻胺光稳定剂HALS 119,0.2kg的三嗪类紫外线吸收剂UV 1577,0.3kg的粒径为30-50nm的纳米氧化锌和0.1kg的硬脂酸钙,将之加入高混机中800rpm混合5min。混合均匀的物料加入预混造粒机,挤出机温控设置为120℃,螺杆长径比为30:1,采用热环切加风冷冷却工艺,得到该配方的高性能耐候复配物。
将100g高性能耐候复配物,20g抗氧剂B215和880gLLDPE树脂混合均匀,然后经过双螺杆挤出机挤出并冷却切粒,得到耐候母粒(A-2)。
实施例3
称量1.6kg的受阻胺光稳定剂HALS 119,0.12kg的三嗪类紫外线吸收剂UV 1577,0.16kg的粒径为30-50nm的纳米氧化锌和0.12kg的硬脂酸钙,将之加入高混机中800rpm混合5min。混合均匀的物料加入预混造粒机,挤出机温控设置为120℃,螺杆长径比为30:1,采用热环切加风冷冷却工艺,得到该配方的高性能耐候复配物。
将100g高性能耐候复配物,20g抗氧剂B215和880gLLDPE树脂混合均匀,然后经过双螺杆挤出机挤出并冷却切粒,得到耐候母粒(A-3)。
对比例1
将100g的光稳定剂HALS 119,20g的抗氧剂B215和880gLLDPE树脂混合均匀,然后经过双螺杆挤出机挤出并冷却切粒,得到耐候母粒(A-4),挤出机温控设置为120℃,螺杆长径比为30:1。
对比例2
称量1.4kg的受阻胺光稳定剂HALS 119,0.5kg的三嗪类紫外线吸收剂UV 1577,0.1kg的硬脂酸钙,加入高混机中800rpm混合5min。混合均匀的物料加入预混造粒机,挤出机温控设置为120℃,螺杆长径比为30:1,采用热环切加风冷冷却工艺,得到该配方的高性能耐候复配物。
将100g高性能耐候复配物,20g抗氧剂B215和880gLLDPE树脂混合均匀,然后经过双螺杆挤出机挤出并冷却切粒,得到耐候母粒(A-5)。
对比例3
称量1.4kg的受阻胺光稳定剂HALS 119, 0.4kg的粒径为30-50nm的纳米氧化锌和0.2kg的硬脂酸钙,将之加入高混机中800rpm混合5min。混合均匀的物料加入预混造粒机,挤出机温控设置为120℃,螺杆长径比为30:1,采用热环切加风冷冷却工艺,得到该配方的高性能耐候复配物。
将100g高性能耐候复配物,20g抗氧剂B215和880gLLDPE树脂混合均匀,然后经过双螺杆挤出机挤出并冷却切粒,得到耐候母粒(A-6)。
薄膜样品制备
将上述实施例1~3制备的耐候母粒A-1~A-3和对比例1~3制备的耐候母粒A-4~A-6按照8%的比例添加到PE吹膜树脂基体中,通过吹膜机吹膜制备8丝(80um)厚的薄膜样品。
性能测试:
将薄膜样品在户外进行耐硫磺熏蒸试验,熏蒸10天(单次硫磺量100g,每日2次),待熏蒸结束后,进行耐候加速试验,测试标准采用GB/T16644.2,具体条件:UV-A灯源,0.76W/m2,8h光照,灯箱60℃;4h黑暗冷凝,灯箱50℃,老化总时长为1000h。测试薄膜样品力学性能,计算处老化后的力学性能保留率,测试结果见表1。
表1薄膜样品耐候加速试验结果
从表1数据可看出,含有普通受阻胺光稳定剂的PE薄膜,不能有效的抵抗酸性环境下的耐候性能,简单复配受阻胺光稳定剂与紫外线吸收剂或无机防晒剂,并不能有效的改善其耐候效果,而本发明的实施例可大幅改善PE薄膜的耐候性能。
实施例4
称量1.2kg的受阻胺光稳定剂HALS 611(HALS 119:HALS 622=2:1),0.4kg的三嗪类紫外线吸收剂UV 1164,0.2kg的粒径为60-80nm的纳米氧化铈和0.2kg的氧化钙,将之加入高混机中800rpm混合5min。混合均匀的物料加入预混造粒机,挤出机温控设置为100℃,螺杆长径比为35,采用热环切加风冷冷却工艺,得到该配方的高性能耐候复配物。
将100g高性能耐候复配物,20g抗氧剂B215和880giPP树脂混合均匀,然后经过双螺杆挤出机挤出并冷却切粒,得到耐候母粒(B-1)。
实施例5
称量1.3kg的受阻胺光稳定剂HALS 611,0.3kg的三嗪类紫外线吸收剂UV 1164,0.3kg的粒径为60-80nm的纳米氧化铈和0.1kg的氧化钙,将之加入高混机中800rpm混合5min。混合均匀的物料加入预混造粒机,挤出机温控设置为100℃,螺杆长径比为35,采用热环切加风冷冷却工艺,得到该配方的高性能耐候复配物。
将100g高性能耐候复配物,20g抗氧剂B215和880giPP树脂混合均匀,然后经过双螺杆挤出机挤出并冷却切粒,得到耐候母粒(B-2)。
实施例6
称量1.5kg的受阻胺光稳定剂HALS 611,0.2kg的三嗪类紫外线吸收剂UV 1164,0.2kg的粒径为60-80nm的纳米氧化铈和0.1kg的氧化钙,将之加入高混机中800rpm混合5min。混合均匀的物料加入预混造粒机,挤出机温控设置为100℃,螺杆长径比为35,采用热环切加风冷冷却工艺,得到该配方的高性能耐候复配物。
将100g高性能耐候复配物,20g抗氧剂B215,和880giPP树脂混合均匀,然后经过双螺杆挤出机挤出并冷却切粒,得到耐候母粒(B-3)。
对比例4
将100g的光稳定剂HALS 611,20g的抗氧剂B215,和880giPP树脂混合均匀,然后经过双螺杆挤出机挤出并冷却切粒,得到耐候母粒(B-4)。
对比例5
将100g光稳定剂UV 1164,20g抗氧剂B215,和880giPP树脂混合均匀,然后经过双螺杆挤出机挤出并冷却切粒,得到耐候母粒(B-5)。
对比例6
称量1.5kg的受阻胺光稳定剂HALS 611,0.4kg的三嗪类紫外线吸收剂UV 1164,0.1kg的氧化钙,将之加入高混机中800rpm混合5min。混合均匀的物料加入预混造粒机,挤出机温控设置为100℃,螺杆长径比为35,采用热环切加风冷冷却工艺,得到该配方的高性能耐候复配物。
将100g高性能耐候复配物,20g抗氧剂B215,和880giPP树脂混合均匀,然后经过双螺杆挤出机挤出并冷却切粒,得到耐候母粒(B-6)。
对比例7
称量1.5kg的受阻胺光稳定剂HALS 611, 0.4kg的粒径为60-80nm的纳米氧化铈和0.1kg的氧化钙,将之加入高混机中800rpm混合5min。混合均匀的物料加入预混造粒机,挤出机温控设置为100℃,螺杆长径比为35,采用热环切加风冷冷却工艺,得到该配方的高性能耐候复配物。
将100g高性能耐候复配物,20g抗氧剂B215和880giPP树脂混合均匀,然后经过双螺杆挤出机挤出并冷却切粒,得到含有光稳定剂的耐候母粒(B-7)。
单丝样品制备
将上述实施例4~6制备的耐候母粒B-1~B-3和对比例4~7制备的耐候母粒B-4~B-7按照5%的比例添加到均聚聚丙烯薄膜级树脂基体中,通过拉丝机制备5丝(50um)厚的单丝样品。
性能测试:
将单丝样品在亚硫酸溶液中(亚硫酸:水=1:4体积比)浸泡15天后,进行耐候加速试验,测试标准采用GB/T16644.2 具体条件: UV-B灯源,0.89W/m2,8h光照,灯箱60℃;4h黑暗冷凝,灯箱50℃,老化总时长为300h。测试单丝样品力学性能,计算处老化后的力学性能保留率,测试结果见表2。
表2单丝样品耐候加速试验结果
由表2数据可知,当与对比例和本领域熟知的复配方案相比,本发明的实施例对聚丙烯单丝制品具有最佳力学性能的防护,且没有影响到树脂的初始性能。
需要说明的是,以上内容仅仅说明了本发明的技术思想,不能以此限定本发明的保护范围,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰均落入本发明权利要求书的保护范围之内。
Claims (10)
1.一种农用聚烯烃薄制品高性能耐候复配物,其特征在于,按质量百分比包括受阻胺光稳定剂50~80%、三嗪类紫外线吸收剂5~20%,无机防晒剂5~20%、吸酸剂5~10%。
2.根据权利要求1所述的一种农用聚烯烃薄制品高性能耐候复配物,其特征在于,所述受阻胺光稳定剂的数均分子量大于2000。
3.根据权利要求2所述的一种农用聚烯烃薄制品高性能耐候复配物,其特征在于,所述受阻胺光稳定剂为HALS 944、HALS 3346、HALS 3529、HALS 119、HALS 2020、HALS 622中的一种或两种。
4.根据权利要求1所述的一种农用聚烯烃薄制品高性能耐候复配物,其特征在于,所述三嗪类紫外线吸收剂为2-(2‘-羟苯基)-1,3,5-三嗪化合物。
5.根据权利要求4所述的一种农用聚烯烃薄制品高性能耐候复配物,其特征在于,所述三嗪类紫外线吸收剂为UV 1577、UV 1164、UV 1600、UV 400中的一种。
6.根据权利要求1所述的一种农用聚烯烃薄制品高性能耐候复配物,其特征在于,所述无机防晒剂的粒径为10~200nm。
7.根据权利要求6所述的一种农用聚烯烃薄制品高性能耐候复配物,其特征在于,所述无机防晒剂为氧化铈、氧化钛、氧化锌、蒙脱土、累托石中的一种。
8.根据权利要求1所述的一种农用聚烯烃薄制品高性能耐候复配物,其特征在于,所述吸酸剂为碱性金属氧化物、叔胺类有机物、硬脂酸盐化合物中的一种。
9.根据权利要求8所述的一种农用聚烯烃薄制品高性能耐候复配物,其特征在于,所述吸酸剂为氧化钙、氧化镁、水滑石、硬脂酸钙、硬脂酸锌、三正十二胺中的一种。
10.一种如权利要求1-9任一项所述农用聚烯烃薄制品高性能耐候复配物的制备方法,其特征在于,包括以下步骤:
S1:将受阻胺光稳定剂、三嗪类紫外线吸收剂、无机防晒剂、吸酸剂在高速混合机中混合,转速为800-1000rpm,时长为2-5min;
S2:将S1所得混合物喂入预混造粒机,工艺温度设置为80~130℃,螺杆长径比为25-40:1,采用热环切加风冷冷却工艺,制得农用聚烯烃薄制品高性能耐候复配物。
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