CN114957865A - 一种抗紫外线橡塑发泡保温材料及制备方法 - Google Patents
一种抗紫外线橡塑发泡保温材料及制备方法 Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 10
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- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 7
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 7
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- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical group C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 6
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- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 5
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- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 claims description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种抗紫外线橡塑发泡保温材料及其制备方法。抗紫外线橡塑发泡保温材料按重量份数计包括以下组份:三元乙丙橡胶15‑25;乙烯‑醋酸乙烯共聚物6‑16;增塑剂15‑25;硫磺0.2‑0.6;硫化促进剂0.7‑1.2;发泡剂10‑15;活性剂2‑4;润滑剂1‑3;炭黑5‑10;阻燃剂15‑25;陶土5‑15;防老剂0.2‑0.5;紫外线吸收剂:0.3‑0.6。该产品在较长时间的紫外光照射下,仍能够保持本身良好的物理力学性能和保温性能等。
Description
技术领域
本发明属于橡塑发泡保温材料技术领域,具体涉及一种抗紫外线橡塑发泡保温材料及制备方法。
背景技术
紫外光老化是指在一定温度、湿度和氧气环境下,高分子材料受到光的长时间照射出现力学性能下降、变色、龟裂和脆化等现象。普通NBR/PVC橡塑发泡材料抗紫外线性能差,在长时间暴露在紫外光照射环境下,很容易出现变形、变色或龟裂、脆化等现象,并且随着时间的推移,物理力学性能出现下降,从而缩短了保温材料的使用寿命,增加了节能保温成本。目前市场上还没有抗紫外性能优异的具有一体化完整结构的橡塑发泡保温产品,有些应用领域为了提高橡塑发泡保温材料的抗紫外线性能,采取了表面涂层或者添加物理复合层的方式。此种方法不仅制作流程比较复杂,加工成本高,而且一定程度上影响了材料的保温效果。
发明内容
为解决现有技术中存在的问题,本发明提供了一种抗紫外线橡塑发泡保温材料及其制备方法,优选出三元乙丙橡胶和乙烯-醋酸乙烯共聚物两种骨架材料进行复合,二者相容性以及加工性能良好,且两种材料本身抗紫外性能优异。此外,配方体系中采用了具有抗紫外性质的几种功能助剂相互配合,在发挥自身作用的同时,与其它助剂间相互协同,使得产品具有优异的抗紫外性能。
在具体应用领域,本发明不仅保证了橡塑保温产品各项性能指标完全满足国家标准,同时,在较长时间紫外光照射以及室外环境等条件下,表现出优异的抗紫外性能。
本发明抗紫外线橡塑发泡保温材料可以为管材、板材或其它异型材。
本发明所述一种抗紫外线橡塑发泡保温材料,按重量份数计包括以下组份:三元乙丙橡胶15-25;乙烯-醋酸乙烯共聚物6-16;增塑剂15-25;硫磺0.2-0.6;硫化促进剂0.7-1.2;发泡剂偶氮二甲酰胺(AC)10-15;活性剂2-4;润滑剂1-3;炭黑5-10;阻燃剂15-25;陶土5-15;防老剂0.2-0.5;紫外线吸收剂:0.3-0.6。
所述增塑剂选自石蜡油和环氧大豆油等。
所述硫化促进剂选自N-环己基-2-苯并噻唑次磺酰胺(CZ)和二硫化四甲基秋兰姆(TMTD)。
所述活性剂选自硬脂酸、纳米氧化锌和对苯亚磺酸锌等。
所述纳米氧化锌按重量份数计含量为1-3份。
所述对苯亚磺酸锌按重量份数计含量为0.2-0.8份。
所述润滑剂选自乙撑双硬脂酰胺和氧化聚乙烯蜡等。
所述润滑剂乙撑双硬脂酰胺与氧化聚乙烯蜡按重量份数计比例为1-2:1。
所述阻燃剂选自十溴二苯乙烷、三氧化二锑、氢氧化铝和有机改性蒙脱土等。
所述阻燃体系各组分配方为十溴二苯乙烷与三氧化二锑按重量份数计比例为2-6:1,氢氧化铝和有机改性蒙脱土按重量份数计比例为2-10:1。
所述防老剂为防老剂4020(N-(1.3-二甲基丁基)-N'-苯基-对苯二胺)和防老剂MB(2-硫醇基苯并咪唑)。
所述防老剂4020和防老剂MB分别作为主、辅防老剂使用。
所述紫外线吸收剂选自二苯甲酮类、苯并三唑类以及三嗪类等。
优选紫外线吸收剂UV531(2-羟基-4-正辛氧基二苯甲酮)和UV329(2-(2'-羟基-5'-特辛基苯基)苯并三唑)。
一种抗紫外线橡塑发泡保温材料的制备方法,包括以下步骤:
(1)混炼胶料的制备
(a)塑炼:将三元乙丙橡胶投入密炼机进行塑炼得到塑炼胶,时间0.5-2min,温度20-60℃。
(b)混炼:将准确称量的乙烯-醋酸乙烯共聚物、增塑剂、发泡剂、润滑剂、炭黑、阻燃剂、防老剂以及紫外线吸收剂等原料进行混合,然后将混合后的原料投入密炼机中与塑炼胶一起进行混炼,时间为3-7min,温度为90℃-120℃。最后加入陶土继续炼胶,时间2-5min,温度140-150℃,得到混炼胶料。
(c)开炼:将步骤(b)得到的混炼胶料投入开炼机中,并加入硫磺、硫化促进剂和活性剂,然后经压片、冷却出片得到成型胶料。
(2)挤出定型
将步骤(1)所述的成型胶料喂入专用挤出设备进行挤出定型,定型模具根据板材或管材等的规格尺寸进行选择。
(3)硫化发泡
将步骤(2)中所述的挤出定型胶输送到自动化硫化发泡炉进行连续发泡生产。
所述硫化发泡工艺中,发泡炉各区温度分别为:一区140-143℃,二区140-143℃,三区145-148℃,四区145-148℃,五区155-158℃,六区160-165℃。
所述发泡炉各区速度为一区0.8-1.2m/min,二区0.9-1.3m/min,三区1.2-1.7m/min,四区1.6-2.8m/min,五区3.3-4.0m/min,六区4.8-5.3m/min。
通过以上(1)-(3)步骤即可得到所述抗紫外线橡塑发泡保温材料。
与现有技术相比,本发明具有以下有益效果:
1、骨架材料。本发明选用的骨架材料为三元乙丙橡胶和乙烯-醋酸乙烯共聚物,其抗紫外性能优于NBR/PVC,优于天然橡胶、其它合成橡胶以及各类橡塑复合材料,且两种材料具有良好的相容性,制备工艺可操作性好。
2、配合助剂。为了延缓发泡保温材料的紫外光降解和其它老化过程,添加了一定量的紫外光吸收剂,使得最终产品的使用寿命大大增加,降低了保温材料成本,节约了能源。本发明优选出两种防老剂和两种紫外光吸收剂进行复配使用,解决了传统橡塑发泡保温材料中仅添加防老剂而抗紫外性能差的缺陷。本发明提供的产品不仅具有一般的抗老化性能,还具有优异的抗紫外光老化性能。产品尤其适用于室外长时间受到光照的设备、管道的保温与防护。
本发明选用的UV531属于二苯甲酮类,UV329属于苯并三唑类,二者复合使用抗紫外效果更好。此外,本体系中的防老剂和抗紫外吸收剂复合使用,对于产品老化和性能衰减表现出了优异的抵抗作用。
本发明采用的硫化促进剂二硫化四甲基秋兰姆(TMTD)为超速级,N-环己基-2-苯并噻唑次磺酰胺(CZ)为准速级,二者搭配使用,在本体系中实现了较好的硫化发泡匹配特性,并且硫化体系中的低单质硫含量也有效提高了产品的抗紫外特性。
本发明所用活性剂纳米氧化锌区别于传统的间接法氧化锌,纳米级氧化锌除了具有高效的活化效果、促进硫化进程,还起到抗紫外辐照老化作用。用量过多会导致严重的硫化发泡不匹配,用量少对产品抗紫外效果不明显。为了有效发挥纳米氧化锌的多重功效,本发明优选含量为1-3份。
相比较于NBR/PVC橡塑发泡材料的氯化石蜡等增塑体系,本发明选择了石蜡油和环氧大豆油作为增塑剂,二者结合使用增塑效果好,耐老化和抗紫外性能优于氯化石蜡等材料,且产品生产过程也更加环保。
本发明所用乙撑双硬脂酰胺和氧化聚乙烯蜡在胶料配方中主要作润滑剂使用,本发明发现体系中不加乙撑双硬脂酰胺,产品容易出现开裂以及起泡现象,添加量多产品较软,大大影响了产品的生产稳定性和产品性能。因此本发明润滑剂用量为1-3份。并且在此使用范围下,产品表观光亮度、产品生产稳定性得到大大改善。
本发明采用的阻燃体系配方不仅具有较好的阻燃性能,也具有较好的抑烟效果,从而满足了各应用领域阻燃标准的要求。
3、制备工艺。本发明制备工艺所需温度和速度要求严苛,发泡炉各区速度过快、温度过低会导致产品交联密度降低,不仅影响产品的物理力学性能,也会降低产品的抗紫外性能。反之,发泡炉各区速度太慢、温度过高不仅影响产品生产效率,也会导致产品过早交联,产品出现开裂现象。因此,在优选的硫化发泡体系下,温度速度需在设定的范围内。
本发明与申请人在先申请201811353839.8相比,本发明在原有基础上进行了配方的改进与优化,并且生产工艺技术也做了优化调整,不仅大大提高了产品的抗紫外性能,而且产品质量更加稳定,生产效率更高。
具体实施方式
下面结合实施例,对本发明做进一步的描述,以下仅为本发明的较佳实施例而已,不能以此限定本发明的范围。即凡是依本发明申请专利范围所作的变化与修饰,皆应仍属本发明专利涵盖的范围内。
对比例选用的是目前市场上CY类B1级NBR/PVC橡塑发泡保温产品,具体为专利号CN103085219A中实施例3所制备的产品。以下是实施例配方表,以及各实施例和对比例测试性能的对比分析。
各实施例的配方如下表1:
表1:实施例1-4配方组成
原料/份数 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
三元乙丙橡胶 | 18 | 19 | 15 | 16 |
乙烯-醋酸乙烯共聚物 | 8 | 7 | 14 | 10 |
石蜡油 | 18 | 18 | 16 | 16 |
环氧大豆油 | 1.5 | 1 | 3 | 3.5 |
硫磺 | 0.5 | 0.6 | 0.4 | 0.3 |
N-环己基-2-苯并噻唑次磺酰胺 | 0.6 | 0.8 | 0.6 | 0.7 |
二硫化四甲基秋兰姆 | 0.4 | 0.3 | 0.2 | 0.4 |
偶氮二甲酰胺 | 13 | 14 | 12 | 11.5 |
纳米氧化锌 | 2.5 | 2.5 | 1.6 | 1.6 |
对苯亚磺酸锌 | 0.5 | 0.5 | 0.3 | 0.3 |
硬脂酸 | 0.8 | 1 | 0.7 | 0.6 |
乙撑双硬脂酰胺 | 1 | 1.2 | 1.2 | 1 |
氧化聚乙烯蜡 | 0.8 | 0.7 | 1.2 | 0.5 |
炭黑 | 7 | 7.3 | 5.8 | 6.3 |
十溴二苯乙烷 | 7.5 | 6.4 | 6 | 6.5 |
三氧化二锑 | 2.5 | 2.4 | 1.5 | 2.5 |
氢氧化铝 | 8 | 8.6 | 8.8 | 8.7 |
有机改性蒙脱土 | 2.5 | 3 | 1 | 3.5 |
陶土 | 6 | 5 | 10 | 9.5 |
防老剂4020 | 0.1 | 0.1 | 0.2 | 0.2 |
防老剂MB | 0.2 | 0.1 | 0.2 | 0.1 |
紫外线吸收剂UV531 | 0.3 | 0.3 | 0.2 | 0.1 |
紫外线吸收剂UV329 | 0.3 | 0.2 | 0.1 | 0.2 |
实施例与对比例抗紫外性能评价:
表2:实施例1-4与对比例性能测试结果
注:紫外光加速老化试验机QUV的检测条件为采用UVA-340灯管,辐照度0.89W/m2/nm,8h紫外光照和4h冷凝交替进行,紫外光照和冷凝循环的温度分别是60℃和50℃。
从表中数据可以看出,室外环境放置4年后,普通NBR/PVC的CY类B1级产品已经严重龟裂,而抗紫外产品仅出现轻微起皱。在快速紫外老化箱中测试240h,普通NBR/PVC的CY类B1产品已经出现变形龟裂,而抗紫外产品无裂纹、无起皱、无变形。在快速紫外老化箱中测试240h后,复测了QUV老化后的导热系数,本发明样品导热系数无明显变化,仍保持良好的绝热保温性能。而对比例样品导热系数数值成倍增加,基本丧失保温性能。
Claims (10)
1.一种抗紫外线橡塑发泡保温材料,按重量份数计包括以下组份:
三元乙丙橡胶15-25;乙烯-醋酸乙烯共聚物6-16;增塑剂15-25;硫磺0.2-0.6;硫化促进剂0.7-1.2;发泡剂偶氮二甲酰胺(AC)10-15;活性剂2-4;润滑剂1-3;炭黑5-10;阻燃剂15-25;陶土5-15;防老剂0.2-0.5;紫外线吸收剂:0.3-0.6。
2.根据权利要求1所述抗紫外线橡塑发泡保温材料,其特征在于,硫化促进剂选自N-环己基-2-苯并噻唑次磺酰胺(CZ)和二硫化四甲基秋兰姆(TMTD)。
3.根据权利要求1或2所述抗紫外线橡塑发泡保温材料,其特征在于,活性剂选自硬脂酸、纳米氧化锌和对苯亚磺酸锌;优选纳米氧化锌按重量份数计含量为1-3份;优选对苯亚磺酸锌按重量份数计含量为0.2-0.8份。
4.根据权利要求1-3所述任意一种抗紫外线橡塑发泡保温材料,其特征在于,润滑剂选自乙撑双硬脂酰胺和氧化聚乙烯蜡;优选乙撑双硬脂酰胺与氧化聚乙烯蜡按重量份数计比例为1-2:1。
5.根据权利要求1-4所述任意一种抗紫外线橡塑发泡保温材料,其特征在于,阻燃剂选自十溴二苯乙烷、三氧化二锑、氢氧化铝和有机改性蒙脱土;优选阻燃体系各组分配方为十溴二苯乙烷与三氧化二锑按重量份数计比例为2-6:1;优选氢氧化铝和有机改性蒙脱土按重量份数计比例为2-10:1。
6.根据权利要求1-5所述任意一种抗紫外线橡塑发泡保温材料,其特征在于,防老剂为防老剂4020(N-(1.3-二甲基丁基)-N'-苯基-对苯二胺)和防老剂MB(2-硫醇基苯并咪唑)。
7.根据权利要求1-6所述任意一种抗紫外线橡塑发泡保温材料,其特征在于,紫外线吸收剂选自二苯甲酮类、苯并三唑类以及三嗪类;优选UV531(2-羟基-4-正辛氧基二苯甲酮)和UV329(2-(2'-羟基-5'-特辛基苯基)苯并三唑)。
8.根据权利要求1-7任意一项所述抗紫外线橡塑发泡保温材料的制备方法,包括以下步骤:
(1)混炼胶料的制备
(a)塑炼:将三元乙丙橡胶投入密炼机进行塑炼得到塑炼胶,时间0.5-2min,温度20-60℃;
(b)混炼:将准确称量的乙烯-醋酸乙烯共聚物、增塑剂、发泡剂、润滑剂、炭黑、阻燃剂、防老剂以及紫外线吸收剂原料进行混合,然后将混合后的原料投入密炼机中与塑炼胶一起进行混炼,时间为3-7min,温度为90℃-120℃;最后加入陶土继续炼胶,时间2-5min,温度140-150℃,得到混炼胶料;
(c)开炼:将步骤(b)得到的混炼胶料投入开炼机中,并加入硫磺、硫化促进剂和活性剂,然后经压片、冷却出片得到成型胶料;
(2)挤出定型
将步骤(1)所述的成型胶料喂入专用挤出设备进行挤出定型;
(3)硫化发泡
将步骤(2)中所述的挤出定型胶输送到自动化硫化发泡炉进行连续发泡生产。
9.根据权利要求8所述抗紫外线橡塑发泡保温材料的制备方法,其特征在于,硫化发泡工艺中,发泡炉各区温度分别为:一区140-143℃,二区140-143℃,三区145-148℃,四区145-148℃,五区155-158℃,六区160-165℃。
10.根据权利要求8或9所述抗紫外线橡塑发泡保温材料的制备方法,其特征在于,发泡炉各区速度为一区0.8-1.2m/min,二区0.9-1.3m/min,三区1.2-1.7m/min,四区1.6-2.8m/min,五区3.3-4.0m/min,六区4.8-5.3m/min。
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