CN113061310A - 一种交联聚氯乙烯结构泡沫材料及其制备方法 - Google Patents

一种交联聚氯乙烯结构泡沫材料及其制备方法 Download PDF

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CN113061310A
CN113061310A CN202110319473.8A CN202110319473A CN113061310A CN 113061310 A CN113061310 A CN 113061310A CN 202110319473 A CN202110319473 A CN 202110319473A CN 113061310 A CN113061310 A CN 113061310A
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polyvinyl chloride
foaming
foam
anhydride
pvc
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CN113061310B (zh
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唐涛
游江岸
姜治伟
薛俭
蒋汉卿
邱健
邢海平
李明罡
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Priority to PCT/CN2021/128051 priority patent/WO2022199029A1/zh
Priority to US18/270,833 priority patent/US20240067788A1/en
Priority to EP21932637.8A priority patent/EP4253476A1/en
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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Abstract

本发明提供了一种物理发泡剂制备交联聚氯乙烯结构泡沫材料的方法，包括：将聚氯乙烯树脂、改性树脂、异氰酸酯、酸酐、成核剂和热稳定剂熔融混合，得到毛坯；将所述毛坯浸渍于发泡气体中发泡，得到发泡体；将所述发泡体进行交联固化，得到交联聚氯乙烯结构泡沫材料。本发明采用全新工艺路线制备交联聚氯乙烯结构泡沫，PVC树脂及其他原材料组成与比例可调范围大；本发明采用二氧化碳或氮气发泡，可以让PVC泡沫制备过程更安全与环保，并能降低成本；本发明制备的泡沫材料具有高的玻璃化转变温度，耐热性能好；本发明制备工艺提高了PVC与其他原材料的相容性或互溶性，材料性能更优。本发明还提供了一种交联聚氯乙烯结构泡沫材料。

Description

一种交联聚氯乙烯结构泡沫材料及其制备方法
技术领域
本发明属于泡沫材料技术领域，尤其涉及一种交联聚氯乙烯结构泡沫材料及其制备方法。
背景技术
泡沫夹芯结构复合材料是一种采用树脂基复合材料作为蒙皮、聚合物泡沫作为芯材的夹芯结构材料，由于其具有强度高、重量轻、刚度大、耐腐蚀、电绝缘、透微波等优异的特性而越来越广泛的被用于航空航天工业的导弹弹翼、直升机侧壁板、风轮叶片等异型件。目前被用作夹芯结构的泡沫芯材主要有交联聚氯乙烯(PVC)结构泡沫、聚苯乙烯(PS)、聚氨酯(PUF)、丙烯腈-苯乙烯(SAN)、聚醚酰亚胺(PEI)及聚甲基丙烯酰亚胺(PMI)等泡沫；其中，交联聚氯乙烯(PVC)结构泡沫由于性能稳定，质地均匀，动静力学性能良好，耐多种化学物质腐蚀，能够适用于承载要求高的部位，而且价格适中，广泛应用于诸多领域，如：风电、轨道交通、建筑、建材、装饰、家具、广告、汽车等行业。
现有技术中交联聚氯乙烯(PVC)结构泡沫的组分主要包括PVC糊树脂、异氰酸酯、酸酐、化学发泡剂；其制备方法为：先将固体物料和液体物料混合得到糊状物料，然后在密封的模具中加压加热，模具内的PVC糊状物料发生凝胶化，发泡剂分解，卸压冷却后，打开模具，得到含有许多泡孔的一次发泡体，然后将一次发泡体在水分存在下进行二次发泡膨胀，同时发生交联固化，最终得到高强度泡沫。现有技术为了便于操作，在生产交联聚氯乙烯结构泡沫时PVC原料一般选用PVC糊树脂，并且要求混合物料以糊状物的状态填入模具中，所以要求液体原料，特别是异氰酸酯的含量较高，导致配方组成比例可调范围受到了限制，进而制约了调节泡沫性能的空间。另外采用PVC糊树脂，降低了原料的适应性，同时成本也较高。
现有技术中一般采用偶氮二异丁腈(AIBN)作为化学发泡剂，但AIBN为易爆有毒试剂，存在环保和安全隐患，并且为了防范安全隐患而导致生产制造成本提高。而且，采用AIBN发泡工艺要求模具必须密封住10～30MPa的压力。虽然可以采用环戊烷等低沸点有机小分子作为发泡剂代替偶氮二异丁腈制备交联PVC结构泡沫，或在配方中加入膨胀微球来降低AIBN的用量和发泡压力；但是对于发泡工艺的要求依然较高。
现有技术制备交联聚氯乙烯结构泡沫一般采用偶氮二甲酰胺(AC)作为成核剂，但是成核剂会残留在体系中，不符合环保要求，而采用碳酸氢钠和碳酸氢钾替代AC，无法实现成核剂在体系中的良好分散，最终会影响成核剂的成核效率和泡孔结构的均匀性。
现有技术在制备交联聚氯乙烯结构泡沫时要求混合物料在模具中升温到170～175℃，保持足够的时间完成模具芯部物料的塑化，然后再降到室温开模，在实际生产中存在一个反复加热和制冷的过程，能耗较大，并且长时间的高温，对体系的热稳定性提出了更高的要求，使得配方调整受限。另外，混合物在模具中加热时，只有液体组分向PVC树脂颗粒内部渗透的过程，所以各组分间的融合程度也会受限，进而影响材料的最终性能。
发明内容
有鉴于此，本发明的目的在于提供一种交联聚氯乙烯结构泡沫及其制备方法，本发明提供的方法工艺简单、安全环保、成本低，制备得到的泡沫材料具有较好的性能。
本发明提供了一种交联聚氯乙烯结构泡沫材料的制备方法，包括：
将聚氯乙烯树脂、改性树脂、异氰酸酯、酸酐、成核剂和热稳定剂熔融混合，得到毛坯；
将所述毛坯浸渍于发泡气体中发泡，得到发泡体；
将所述发泡体进行交联固化，得到交联聚氯乙烯结构泡沫材料。
优选的，所述改性树脂选自聚甲基丙烯酸甲酯、甲基丙烯酸甲酯-丙烯酸丁酯共聚物、苯乙烯-丙烯腈共聚物、氯化聚氯乙烯、氯化聚乙烯和热塑性聚氨酯中的一种或几种。
优选的，所述异氰酸酯选自甲苯二异氰酸酯、碳化二亚胺-脲酮亚胺改性4,4’-二苯基甲烷二异氰酸酯和多亚甲基多苯基多异氰酸酯中的一种或几种。
优选的，所述酸酐选自邻苯二甲酸酐、马来酸酐、琥珀酸酐、四氢苯酐、六氢苯酐、甲基四氢苯酐、甲基六氢苯酐、偏苯三甲酸酐和均苯四酐中的一种或几种。
优选的，所述成核剂选自纳米二氧化硅、炭黑、煅烧高岭土、分子筛、超细硅酸铝、碳酸钙和玻璃粉中的一种或几种。
优选的，所述热稳定剂选自硬脂酸钙、硬脂酸锌、硬脂酸钡、有机锡热稳定剂、三盐基硫酸铅、二盐基亚磷酸铅、环氧大豆油和环氧树脂中的一种或几种。
优选的，所述发泡气体选自二氧化碳或氮气。
优选的，得到发泡体的方法包括：
在压力作用下，所述毛坯浸渍于发泡气体中，然后通过卸压，得到发泡体；
所述压力为6～15MPa。
优选的，所述聚氯乙烯树脂、改性树脂、异氰酸酯、酸酐、成核剂和热稳定剂的质量比为100：(0～50)：(30～150)：(0～80)：(0～5)：(1～5)。
本发明提供了一种上述技术方案所述的方法制备得到的交联聚氯乙烯结构泡沫材料。
本发明提供的交联聚氯乙烯结构泡沫材料的制备方法具有显著的优点：本发明采用的发泡方法不受现有技术对糊状物料的工艺要求限制，可以混合不同性状的聚合物实现发泡；本发明采用熔融混合以及气体物理发泡的方法极大的提高了各组分间的融合，提高了泡沫材料的玻璃化转变温度和泡孔结构的均匀性；本发明在制备交联聚氯乙烯泡沫材料的整个工艺过程中，PVC经历的高温热时间大大缩短，对体系的热稳定性要求大大降低；本发明采用二氧化碳或氮气等发泡气体为发泡剂，无机组分为成核剂，没有AIBN分解残余物和AC残留，工艺和产品环保，成本低；本发明的制备方法采用熔融混合时间短，发泡剂浸渍发泡温度低，工艺整体能耗大大降低。
附图说明
图1为本发明比较例1制备的泡沫材料的扫描电镜图；
图2为本发明比较例1制备的泡沫材料的动态热机械分析曲线；
图3为本发明实施例1制备的泡沫材料的扫描电镜图；
图4为本发明实施例1制备的泡沫材料的动态热机械分析曲线。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员经改进或润饰的所有其它实例，都属于本发明保护的范围。应理解，本发明实施例仅用于说明本发明的技术效果，而非用于限制本发明的保护范围。实施例中，所用方法如无特别说明，均为常规方法。
本发明提供了一种交联聚氯乙烯结构泡沫材料的制备方法，包括：
将聚氯乙烯树脂、改性树脂、异氰酸酯、酸酐、成核剂和热稳定剂熔融混合，得到毛坯；
将所述毛坯浸渍于发泡气体中发泡，得到发泡体；
将所述发泡体进行交联固化，得到交联聚氯乙烯结构泡沫材料。
现有技术一般采用乳液聚合工艺生产的PVC树脂(聚氯乙烯树脂，又称为PVC糊树脂)作为主要原料之一制备交联聚氯乙烯结构泡沫。相对于PVC糊树脂，采用悬浮聚合工艺生产的疏松型PVC树脂(又称为PVC悬浮树脂)具备成本低廉的优点。现有技术制备交联聚氯乙烯结构泡沫所采用的聚氯乙烯树脂一般为PVC糊树脂，不采用疏松型PVC悬浮树脂，这是由于疏松型PVC悬浮树脂吸油值高，对液体吸收能力强，当固体物料和液体物料混合时，不能形成均匀的糊状物料，只能形成湿的粉状物料；如果直接将这种湿的粉状物料放入模具中模压，粉状物料中的液体原料会从模具缝隙流出。
本发明采用了全新的制备工艺路线，第一步采用熔融混合工艺，可以快速实现PVC的塑化过程，替代了现有技术中依赖于长时间静态温度升高完成PVC树脂颗粒吸收液态物料的塑化工艺过程。本发明提供的工艺方法对PVC树脂没有特别的要求，可以全部采用价格较低的PVC悬浮树脂，显著降低了原材料成本。
在本发明中，所述改性树脂优选选自聚甲基丙烯酸甲酯、甲基丙烯酸甲酯-丙烯酸丁酯共聚物、苯乙烯-丙烯腈共聚物、氯化聚氯乙烯、氯化聚乙烯和热塑性聚氨酯中的一种或几种。本发明采用改性树脂可以调整制备得到的PVC结构泡沫材料的性能，现有技术制备PVC结构泡沫材料很难将上述改性树脂加入到PVC结构泡沫中；本发明通过采用熔融混合工艺，使改性树脂可以添加到PVC结构泡沫中，实现对泡沫结构和性能的调整。
在本发明中，所述异氰酸酯优选选自甲苯二异氰酸酯(TDI)、碳化二亚胺-脲酮亚胺改性4,4‘-二苯基甲烷二异氰酸酯(CD-MDI)和多亚甲基多苯基多异氰酸酯(PMDI)中的一种或几种。
在本发明中，所述酸酐优选选自邻苯二甲酸酐(PA)、马来酸酐(MA)、琥珀酸酐(SA)、四氢苯酐(THPA)、六氢苯酐(HHPA)、甲基四氢苯酐(MTHPA)、甲基六氢苯酐(MHHPA)、偏苯三甲酸酐(TMA)和均苯四酐(PDMA)中的一种或几种。
在本发明中，所述成核剂优选选自纳米二氧化硅、炭黑、煅烧高岭土、分子筛、超细硅酸铝、碳酸钙和玻璃粉中的一种或几种。
在本发明中，所述热稳定剂优选选自硬脂酸钙、硬脂酸锌、硬脂酸钡、有机锡热稳定剂、三盐基硫酸铅、二盐基亚磷酸铅、环氧大豆油和环氧树脂中的一种或几种。
在本发明中，所述聚氯乙烯树脂、改性树脂、异氰酸酯、酸酐、成核剂和热稳定剂的质量比优选为100：(0～50)：(30～150)：(0～80)：(0～5)：(1～5)，更优选为100：(10～40)：(50～120)：(10～60)：(1～4)：(2～4)，最优选为100：(20～30)：(80～100)：(20～50)：(2～3)：2.5。
在本发明中，所述熔融混合的温度优选为130～170℃，更优选为140～160℃，最优选为150℃。
在本发明中，得到发泡体的方法优选包括：
在压力作用下，将所述毛坯浸渍于发泡气体中然后卸压，得到发泡体。
在本发明中，得到发泡体的方法更优选包括：
在压力作用下，将所述毛坯置于密封腔体中，浸渍于发泡气体中然后卸压，得到发泡体。
在本发明中，得到发泡体的方法最优选包括：
在温度和压力的作用下，将所述毛坯浸渍于发泡气体中然后卸压，得到发泡体。
在本发明中，所述温度优选为25～125℃，更优选为40～110℃，更优选为60～95℃，更优选为70～85℃，最优选为75～80℃。在本发明中，所述压力优选为6～15MPa，更优选为10～13MPa。
在本发明中，所述发泡气体优选为二氧化碳或氮气。
在本发明中，所述卸压之前的保压时间优选为20～50min/mm(每毫米厚毛坯保压20～50min)，更优选为30～40min/mm。
在本发明中，所述卸压即为排掉发泡气体的过程。
在本发明中，所述交联固化之前优选还包括：
将发泡体进行膨胀。
在本发明中，所述膨胀优选在热空气、热水或饱和水蒸气中进行；所述膨胀的温度优选为70～99℃，更优选为75～95℃，更优选为80～95℃，最优选为85～95℃。
在本发明中，所述交联固化优选在饱和水蒸气或热水中进行；所述交联固化的温度优选为40～70℃，更优选为50～60℃；所述交联固化的时间优选为4～6天，更优选为5天。
本发明提供的交联聚氯乙烯结构泡沫材料的制备方法具有显著的优点：本发明采用的发泡方法不受现有技术对糊状物料的工艺要求限制，可以混合不同性状的聚合物实现发泡；本发明采用熔融混合方法极大的提高了各组分间的融合，提高了泡沫材料的玻璃化转变温度和泡孔结构的均匀性；本发明在制备交联聚氯乙烯泡沫材料的整个工艺过程中，PVC经历的高温热时间大大缩短，对体系的热稳定性要求大大降低；本发明采用二氧化碳或氮气等发泡气体为发泡剂，无机组分为成核剂，没有AIBN分解残余物和AC残留，工艺和产品环保，成本低；本发明的制备方法采用熔融混合时间短，发泡剂浸渍发泡温度低，工艺整体能耗大大降低。
本发明以下实施例和比较例所采用原料均为市售产品。
比较例1
将100g PVC树脂(糊树脂)、60g PMDI、30g MHHPA、10g AIBN、2g AC(偶氮二甲酰胺)、2g硬脂酸钙室温混合成糊状料，加入12mm厚的模腔中，在175℃、16MPa压力下保持10分钟，然后冷却至25℃开模，得到一次发泡体；将一次发泡体放入95℃热水中进行膨胀30分钟，得到二次发泡体；将二次发泡体置于60℃的饱和水蒸气中交联固化4天，得到交联PVC结构泡沫材料。
对比较例1制备得到的交联PVC结构泡沫材料进行扫描电镜检测，检测结果如图1所示，比较例1制备的泡沫材料的密度为70kg/cm3，平均泡孔尺寸约450μm。
对比较例1制备的交联PVC结构泡沫材料进行动态热机械分析，检测结果如图2所示，比较例1制备的泡沫材料的玻璃化转变温度为81.2℃。
泡沫材料的密度(ρf)采用排水法测定：
首先用电子天平测得泡沫样品的重量mf，然后把泡沫样品浸没入水中，当泡沫样品刚好完全浸入水中时，再次利用电子天平得到体系增加的重量为m0，最后ρf＝mf/(m0/ρ水)，其中ρ水是水的质量密度。
泡沫的泡孔结构采用扫描电子显微镜(XL30 ESEM,PHILLIPS)拍摄，并采用图片处理软件(Nano Measurer)统计平均泡孔直径。
泡沫材料的玻璃化转变温度是通过采用动态热机械分析仪(Metravib DMA 450Newtons)以频率为1.0Hz、升温速率为5℃/min、温度范围为室温至150℃条件下对泡沫材料样品进行拉伸测试，得到损耗角正切值(tanδ)-温度关系曲线，取其曲线的最大峰值所对应的温度得到。
实施例1
将100g PVC树脂(糊树脂)、60g PMDI、30g MHHPA、2.0g煅烧高岭土、2g硬脂酸钙在150℃下熔融混合得到6mm厚的毛坯；然后将毛坯放入到90℃的密封腔体中，通入二氧化碳升压至10MPa，保压120min，排掉二氧化碳，得到一次发泡体；将一次发泡体浸于90℃的热水中进行二次膨胀6min，得到二次发泡体；将二次发泡体置于60℃的饱和水蒸气中交联固化4天，得到交联PVC结构泡沫材料。
按照比较例1的方法对本发明实施例1制备的交联PVC结构泡沫进行检测，检测结果如图3所示，实施例1制备的泡沫材料的密度为70kg/cm3，平均泡孔尺寸约90μm。
按照比较例1的方法对实施例1制备的泡沫材料进行动态热机械分析，检测结果如图4所示，实施例1制备的泡沫材料的玻璃转变温度为98.4℃。
与比较例1对比可以看出，采用熔融混合后再用物理发泡剂浸渍发泡，可以获得更小的泡孔直径和更高的玻璃化转变温度。
实施例2
将100g PVC树脂、30g PMMA(聚甲基丙烯酸甲酯)、100g TDI、60g PA、0.6g硬脂酸钙、0.4g硬脂酸锌、1.0g纳米二氧化硅，0.5g分子筛在150℃熔融混合得到厚度为6mm的毛坯；将毛坯放入到125℃的密封腔体中，通入二氧化碳升压至6MPa，保压120min，排掉二氧化碳，得到PVC一次发泡体；将一次发泡体浸于95℃的热水中进行二次膨胀30min，得到二次发泡体；将二次发泡体置于40℃的热水中交联固化6天，得到交联PVC结构泡沫材料。
按照比较例1的方法对本发明实施例2制备的交联PVC结构泡沫进行检测，泡沫材料的密度为50kg/cm3，平均泡孔尺寸约95μm，泡沫材料的玻璃转变温度为100.3℃。
实施例3
将100g PVC树脂、10g ACR(甲基丙烯酸甲酯-丙烯酸丁酯共聚物)、120g CD-MDI、30g MA、5.0g硬脂酸钡、3.0g煅烧高岭土在150℃熔融混合得到厚度为6mm的毛坯；将毛坯放入到25℃的密封腔体中，通入二氧化碳升压至15MPa，保压300min，排掉二氧化碳，得到PVC一次发泡体；将一次发泡体浸于99℃的热空气中进行二次膨胀20min，得到二次发泡体；将二次发泡体置于70℃的饱和水蒸气中交联固化4天，得到交联PVC结构泡沫材料。
按照比较例1的方法对本发明实施例3制备的交联PVC结构泡沫进行检测，泡沫材料的密度为33kg/cm3，平均泡孔尺寸约80μm，泡沫材料的玻璃转变温度为94.2℃。
实施例4
将100g PVC树脂、10g SAN(苯乙烯-丙烯腈共聚物)、30g CD-MDI、20g THPA、3.0g有机锡热稳定剂、1.0环氧大豆油、5.0g分子筛在150℃熔融混合得到厚度为6mm的毛坯；将毛坯放入到95℃的密封腔体中，通入氮气升压至10MPa，保压120min，排掉氮气，得到PVC一次发泡体；将一次发泡体浸于95℃的饱和水蒸气中进行二次膨胀40min，得到二次发泡体；将二次发泡体置于60℃的饱和水蒸气中交联固化4天，得到交联PVC结构泡沫材料。
按照比较例1的方法对本发明实施例4制备的交联PVC结构泡沫进行检测，泡沫材料的密度为90kg/cm3，平均泡孔尺寸约86μm，泡沫材料的玻璃转变温度为97.6℃。
实施例5
将100g PVC树脂、30g CPE(氯化聚乙烯)、20g TPU(热塑性聚氨酯)、150g CD-MDI、10g SA、20g HHPA、25g TMA、3.0g三盐基硫酸铅、2.0g二盐基亚磷酸铅、1.0g炭黑、2.0g煅烧高岭土在150℃熔融混合得到厚度为6mm的毛坯；将毛坯放入到65℃的密封腔体中，通入二氧化碳升压至12MPa，保压120min，排掉二氧化碳，得到PVC一次发泡体；将一次发泡体浸于95℃的热水中进行二次膨胀30min，得到二次发泡体；将二次发泡体置于60℃的热水中交联固化4天，得到交联PVC结构泡沫材料。
按照比较例1的方法对本发明实施例5制备的交联PVC结构泡沫进行检测，泡沫材料的密度为38kg/cm3，平均泡孔尺寸约97μm，泡沫材料的玻璃转变温度为92.5℃。
实施例6
将100g PVC树脂、15g TPU、15g CPVC(氯化聚氯乙烯)、30g TDI、30g CD-MDI、30gPMDI、30g MTHPA、30g MHHPA、10g PDMA、2.0g超细硅酸铝、2.0g碳酸钙、1.0g玻璃粉、0.6g三盐基硫酸铅、0.4g硬脂酸钡、1.0g环氧树脂在150℃熔融混合得到厚度为6mm的毛坯；将毛坯放入到85℃的密封腔体中，通入氮气升压至8MPa，保压120min，排掉氮气，得到PVC一次发泡体；将一次发泡体浸于70℃的热空气中进行二次膨胀50min，得到二次发泡体；将二次发泡体置于60℃的热水中交联固化4天，得到交联PVC结构泡沫材料。
按照比较例1的方法对本发明实施例6制备的交联PVC结构泡沫进行检测，泡沫材料的密度为60kg/cm3，平均泡孔尺寸约93μm，泡沫材料的玻璃转变温度为100.1℃。
实施例7
将100gPVC树脂、100g PMDI、30g TPU、1.0g硬脂酸钙、2.0g硬脂酸钡在150℃熔融混合得到厚度为6mm的毛坯；将毛坯放入到90℃的密封腔体中，通入二氧化碳升压至10MPa，保压120min，排掉二氧化碳，得到PVC一次发泡体；将一次发泡体浸于90℃的热水中进行二次膨胀30min，得到二次发泡体；将二次发泡体置于60℃的热水中交联固化4天，得到交联PVC结构泡沫材料。
按照比较例1的方法对本发明实施例7制备的交联PVC结构泡沫进行检测，泡沫材料的密度为46kg/cm3，平均泡孔尺寸约140μm，泡沫材料的玻璃转变温度为98.3℃。
实施例8
将100g PVC树脂、20g PMMA、20g CPE、10g ACR、80g PMDI、70g CD-MDI、80gMHHPA、2.0g煅烧高岭土、1.0g玻璃粉、1.0g有机锡热稳定剂、2g环氧树脂在150℃熔融混合得到厚度为6mm的毛坯；将毛坯放入到55℃的密封腔体中，通入二氧化碳升压至10MPa，保压120min，排掉二氧化碳，得到PVC一次发泡体；将一次发泡体置于50℃的热水中交联固化5天，得到交联PVC结构泡沫材料。
按照比较例1的方法对本发明实施例8制备的交联PVC结构泡沫进行检测，泡沫材料的密度为80kg/cm3，平均泡孔尺寸约60μm，泡沫材料的玻璃转变温度为97.8℃。
本发明提供的交联聚氯乙烯结构泡沫材料的制备方法具有显著的优点：本发明采用的发泡方法不受现有技术对糊状物料的工艺要求限制，可以混合不同性状的聚合物实现发泡；本发明采用熔融混合方法极大的提高了各组分间的融合，提高了泡沫材料的玻璃化转变温度和泡孔结构的均匀性；本发明在制备交联聚氯乙烯泡沫材料的整个工艺过程中，PVC经历的高温热时间大大缩短，对体系的热稳定性要求大大降低；本发明采用二氧化碳或氮气等发泡气体为发泡剂，无机组分为成核剂，没有AIBN分解残余物和AC残留，工艺和产品环保，成本低；本发明的制备方法采用熔融混合时间短，发泡剂浸渍发泡温度低，工艺整体能耗大大降低。
以上所述的仅是本发明的优选实施方式，应当指出，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(例如可以加入阻燃剂、表面活性剂、填料和颜料等)，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

1.一种交联聚氯乙烯结构泡沫材料的制备方法，包括：
将聚氯乙烯树脂、改性树脂、异氰酸酯、酸酐、成核剂和热稳定剂熔融混合，得到毛坯；
将所述毛坯浸渍于发泡气体中发泡，得到发泡体；
将所述发泡体进行交联固化，得到交联聚氯乙烯结构泡沫材料。
2.根据权利要求1所述的方法，其特征在于，所述改性树脂选自聚甲基丙烯酸甲酯、甲基丙烯酸甲酯-丙烯酸丁酯共聚物、苯乙烯-丙烯腈共聚物、氯化聚氯乙烯、氯化聚乙烯和热塑性聚氨酯中的一种或几种。
3.根据权利要求1所述的方法，其特征在于，所述异氰酸酯选自甲苯二异氰酸酯、碳化二亚胺-脲酮亚胺改性4,4’-二苯基甲烷二异氰酸酯和多亚甲基多苯基多异氰酸酯中的一种或几种。
4.根据权利要求1所述的方法，其特征在于，所述酸酐选自邻苯二甲酸酐、马来酸酐、琥珀酸酐、四氢苯酐、六氢苯酐、甲基四氢苯酐、甲基六氢苯酐、偏苯三甲酸酐和均苯四酐中的一种或几种。
5.根据权利要求1所述的方法，其特征在于，所述成核剂选自纳米二氧化硅、炭黑、煅烧高岭土、分子筛、超细硅酸铝、碳酸钙和玻璃粉中的一种或几种。
6.根据权利要求1所述的方法，其特征在于，所述热稳定剂选自硬脂酸钙、硬脂酸锌、硬脂酸钡、有机锡热稳定剂、三盐基硫酸铅、二盐基亚磷酸铅、环氧大豆油和环氧树脂中的一种或几种。
7.根据权利要求1所述的方法，其特征在于，所述发泡气体选自二氧化碳或氮气。
8.根据权利要求1所述的方法，其特征在于，得到发泡体的方法包括：
在压力作用下，所述毛坯浸渍于发泡气体中，然后通过卸压，得到发泡体；
所述压力为6～15MPa。
9.根据权利要求1所述的方法，其特征在于，所述聚氯乙烯树脂、改性树脂、异氰酸酯、酸酐、成核剂和热稳定剂的质量比为100：(0～50)：(30～150)：(0～80)：(0～5)：(1～5)。
10.一种权利要求1所述的方法制备得到的交联聚氯乙烯结构泡沫材料。
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