CN111647129A - 用于制备聚氨酯仿乳胶海绵的组合物、仿乳胶海绵及其制备方法 - Google Patents
用于制备聚氨酯仿乳胶海绵的组合物、仿乳胶海绵及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种用于制备聚氨酯仿乳胶海绵的组合物、仿乳胶海绵及其制备方法,组合物包括如下重量份的原料:伯羟基聚醚70‑90份;聚合物聚醚10‑30份;交联剂0.5‑2.5份;甲苯二异氰酸酯20‑30份;其中,NCO反应指数为0.8‑1.05,伯羟基聚醚为PO/EO共聚醚多元醇,伯羟基聚醚中环氧乙烷质量含量为10‑20%,伯羟基比例为70‑85%,重均分子量为4500‑7500;聚合物聚醚为苯乙烯‑丙烯腈聚合物接枝改性的伯羟基聚醚,且苯乙烯‑丙烯腈聚合物在聚合物聚醚中的含量为20‑45%。通过选择合适的组分和含量,可以制得性能优异的仿乳胶海绵。
Description
技术领域
本发明涉及聚氨酯软质泡沫领域,具体涉及一种用于制备聚氨酯仿乳胶海绵的组合物、聚氨酯仿乳胶海绵及其制备方法。
背景技术
乳胶海绵由于其柔软和亲肤的表面触感,良好的回弹和支撑性,优异的耐压缩疲劳,舒适耐久以及多孔的透气性结构被公认为是用于家具类的沙发床垫以及枕头,化妆用品的化妆棉以及粉扑的高端材料。乳胶海绵的生产配方所使用的主体材料为天然乳胶,也通常需要和有机合成类的丁苯乳胶、氯丁乳胶、丁晴乳胶等混合使用,用以提到产品性能和性价比,除此之外,乳胶海绵的配方中还会用到硫化剂、促进剂、防老剂、稳定剂等化学助剂。乳胶海绵有两种常见的制造方法,邓禄普法(又称机械打泡法或迟缓凝胶法)和塔勒莱法(又称真空发泡法),通常包括9步生产工序,涉及大型定制化模具设备,高温115℃硫化,低温-30℃冷冻,半成品通过多次水洗清洁海绵制品残留的化学试剂含量,制品烘干除去残留水分等关键步骤。工艺过程复杂,耗时长,耗费能源和水,人力和设备资源投入较大。
由于乳胶海绵配方涉及主原料的单一性,实际生产可供操作的配方调整宽容度非常窄,产品物性主要跟海绵的密度相关,密度越高,各方面的物性指标越好,硬度也相对越高。因此由此制造的乳胶海绵本身产品密度(不低于50kg/m3)和成本均高于聚氨酯海绵材料,且乳胶海绵使用一段时间后还易吸潮老化,泡沫出现表面硬化开裂,泡沫体粉化、强度变差等问题。
因此,聚氨酯海绵作为乳胶海绵的竞争材料具有诸多不可忽视的优势。已有专利文献公开了仿乳胶海绵的聚氨酯海绵的制备方法,如:中国专利CN108129629A公开了一种乳胶手感聚氨酯软质泡沫及其制备方法,其原料包括异氰酸酯、聚醚多元醇、水、物理发泡剂、胺催化剂、硒催化剂、有机硅表面活性剂和手感促进剂,通过在产品组分中使用手感促进剂和聚醚多元醇组合,使得产品配方宽容度增大,手感提高,回弹性增加,生产稳定,解决了高回弹和高表面硬度并存,不能同时实现低表面硬度、柔软手感和高回弹性的问题,该技术方案中聚醚多元醇成分复杂且以碳酸钙为手感促进剂,在聚氨酯配方中使用碳酸钙会导致成品泡沫的拉伸强度、撕裂强度、支撑因子以及压缩变定等性能变差,并且该技术方案中需要使用物理发泡剂以降低泡沫的密度。
中国专利CN110283293A公开了一种采用端异氰酸酯基预聚体制备的仿乳胶聚氨酯软质泡沫,其通过聚醚多元醇改性单体MDI二苯基亚甲基二异氰酸酯,再和聚合MDI多苯基多亚甲基多异氰酸酯掺混得到异氰酸酯基的质量百分比为24~29%的端异氰酸酯基预聚体,再与含催化剂、硅油表面活性剂以及物理发泡剂的多元醇组合物反应制得聚氨酯仿乳胶海绵。
中国专利CN109679069A公开了一种仿乳胶超软高回弹海绵,其将纯4,4’-二苯基甲烷二异氰酸酯与聚醚多元醇反应得到预聚体;再由预聚体与多苯基多亚甲基多异氰酸酯反应制得的混合物,用灌注机和模具间歇式生产各种模塑成型海绵。专利CN110283293A和专利CN109679069A在生产过程中,均需通过聚醚多元醇对商品化的异氰酸酯原料进行预聚合改性且配方中均含有物理发泡剂用于降低海绵密度以及软化制品,制备工艺复杂、环保性能差。
发明内容
因此,本发明要解决的技术问题在于克服现有技术中制备具有低表面硬度和高回弹性能的仿乳胶海绵时需要使用手感促进剂、且为了降低海绵密度需要使用物理发泡剂的缺陷,从而提供一种用于制备聚氨酯仿乳胶海绵的组合物。
本发明还提供一种聚氨酯仿乳胶海绵。
本发明还提供一种聚氨酯仿乳胶海绵的制备方法。
因此,本发明提供一种用于制备聚氨酯仿乳胶海绵的组合物,包括如下重量份的原料:
伯羟基聚醚 70-90份;
聚合物聚醚 10-30份;
交联剂 0.5-2.5份;
甲苯二异氰酸酯 20-30份;
其中,NCO反应指数为0.8-1.05,所述伯羟基聚醚为PO/EO共聚醚多元醇,所述伯羟基聚醚中环氧乙烷质量含量为10-20%,伯羟基比例为70-85%,重均分子量为4500-7500;所述聚合物聚醚为苯乙烯-丙烯腈聚合物接枝改性的伯羟基聚醚,且苯乙烯-丙烯腈聚合物在聚合物聚醚中的含量为20-45%。
具体的,所述伯羟基聚醚可以为以含活性氢的三官能度小分子醇类比如甘油或三羟甲基丙烷等作为起始剂与环状单体环氧丙烷和环氧乙烷聚合合成的聚醚多元醇。
优选的,该成品伯羟基聚醚需要经过水洗等后处理工序降低小分子醇、醛类残留,得到低气味型的伯羟基高活性聚醚。聚合物聚醚为低气味型高活性聚合物聚醚。
所述聚合物聚醚为以上述的伯羟基聚醚为基础聚醚,以苯乙烯-丙烯腈聚合物为接枝共聚改性聚合物对伯羟基聚醚进行接枝改性制备得到。
进一步地,所述交联剂为两官能度或三官能度的醇和/或醇胺。
进一步地,所述交联剂为乙二醇、二丙二醇、1,4-丁二醇、甘油、二乙醇胺和三乙醇胺中的一种或几种。
进一步地,所述甲苯二异氰酸酯为80wt%的2,4-甲苯二异氰酸酯和20wt%的2,6-甲苯二异氰酸酯的混合物。
进一步地,还包括原料:水1.4-2.3份;表面活性剂0.5-1.5份;催化剂0.12-1.1份;助剂0-4份。
进一步地,所述水为去离子水。
进一步地,所述表面活性剂为聚醚改性聚硅氧烷。
进一步地,所述催化剂为胺类催化剂和有机金属类催化剂的混合物。
进一步地,所述胺类催化剂为含端羟基或端氨基的叔胺、苄胺和/或吗啉类催化剂,所述有机金属类催化剂为机金属锡类、有机铋类和/或有机锌类催化剂。
进一步地,所述助剂为阻燃剂、亲水剂、色浆和/或抗菌剂,上述助剂均为商业化的用于聚氨酯软质泡沫产品的功能性助剂。
进一步地,所述NCO反应指数为异氰酸酯基团和羟基基团的摩尔比。
本发明还提供一种聚氨酯仿乳胶海绵的制备方法,将原料伯羟基聚醚、聚合物聚醚、交联剂、水、表面活性剂、催化剂、甲苯二异氰酸酯和助剂同时加入到反应器内,并向反应器内通入干燥的空气或惰性气体,将原料进行搅拌混合,并同时进行发泡反应,然后熟化,碾压破孔,得到产品。
进一步地,搅拌混合时压力为1.0-2.0bars、搅拌速度为4000-5000rpm/min,搅拌时间为2-6s,干燥的空气或惰性气体的通入速度为50-200ml/min。
具体的,配方里的各原料分别单独存放在密闭储罐或半开放式储罐且控制料温在22-25℃,通过计量泵按配方比例将各原料同时抽入带混合室和锯齿状搅拌棒的搅拌机头,除此之外还需要往混合室注入一定量的干燥空气或氮气(50-200ml/min),在设定好的混合室压力(1.0-2.0bars)、搅拌棒转速(4000-5000rpm/min)、搅拌时间(2-6secs)的条件下混合好物料,从混合机头出来的物料经由金属溢流槽或摆头装置流出,均匀分布在铺好底纸和侧纸的移动传送带上,物料沿着倾斜的跌落板向下流动且向上发泡,并按照一定的传送带速度(3.0-5.0m/min)向前移动,泡沫移动到跌落板装置后0.5-2.0米处达到最高点且上表面呈水平状态,经过一段烘道加热熟化后,连续状海绵被切断成一定长度(3-10米)的块状。块状海绵放入室内常温仓库继续熟化24-48小时后,可根据要求裁切成不同尺寸和形状,裁切之后的半成品需要使用双辊破孔机进行机械碾压破孔,最终得到具有乳胶类似物性的低气味聚氨酯仿乳胶海绵制品。
本发明技术方案,具有如下优点:
1.本发明提供的用于制备聚氨酯仿乳胶海绵的组合物,包含伯羟基聚醚、聚合物聚醚、交联剂和甲苯二异氰酸酯,其中,NCO反应指数为0.8-1.05,伯羟基聚醚为PO/EO共聚醚多元醇,伯羟基聚醚中环氧乙烷质量含量为10-20%,伯羟基比例为70-85%,重均分子量为4500-7500;聚合物聚醚为苯乙烯-丙烯腈聚合物接枝改性的所述伯羟基聚醚,且苯乙烯-丙烯腈聚合物在聚合物聚醚中的含量为20-45%,该原料组合物通过协同作用可以实现只采用水作为发泡剂,不用物理发泡剂即可使得最终产品具有手感柔软舒适、较低的密度、高回弹性和低表面硬度的性能,并且其他性能也能达到乳胶海绵的标准,甚至具有更为优异的物理机械性能,还使整个产品的生产和使用更健康环保。具体的,制得的仿乳胶海绵气味低,回弹、舒适因子变形、手感相当于乳胶棉,拉伸、撕裂强度性能、永久压缩和透气性能优于乳胶棉,甚至可以制得密度更低的产品而节省成本。同时,该配方体系方便根据产品性能要求进行调整,可以直接采用一步法连续线大块泡工艺(Slabstock)进行生产,工艺简单,能耗低,无需重复投资模具或其它工装设备,高效(产量可达到200-500kg/min)。
2.本发明提供的聚氨酯仿乳胶海绵,TDI结构中异氰酸酯的质量百分比高,海绵发泡倍率相应也高,而更低的苯环含量使得制得的海绵制品也更柔顺,拉伸强度、撕裂强度和断裂延伸率都相对更高,制备的海绵触感更柔软,回弹性更好。
3.本发明提供的聚氨酯仿乳胶海绵,原料简单、廉价、易得且无需特殊预处理,低气味型聚醚+反应型胺类催化剂的全水搭配组合也极大的降低聚氨酯海绵制品的VOC残留和难闻的气味性,提高产品的健康环保性;所运用的配方体系,方便根据产品性能要求调整。
4.本发明提供的聚氨酯仿乳胶海绵的制备方法,通过一步法直接将所有组份搅拌均匀后经由一步法连续线大块泡工艺(Slabstock)发泡成型,海绵熟化后经由切割机裁切称所需的形状,无需根据最终用户对海绵制品尺寸或造型上的要求重新投资模具等工装费用,节省成本。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明,并不局限于所述最佳实施方式,不对本发明的内容和保护范围构成限制,任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品,均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者,按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规试剂产品。
以下实施例和对比例中所用到的原料有:
伯羟基聚醚
佳化化学股份有限公司Lodour 4800,重均分子量约4800,环氧乙烷质量含量为15%,伯羟基比例为75%。
佳化化学股份有限公司Lodour 6000,重均分子量约6000,环氧乙烷质量含量为15%,伯羟基比例为85%。
佳化化学股份有限公司Lodour 7000,重均分子量约7000,环氧乙烷质量含量15%,伯羟基比例为85%。
聚合物聚醚
佳化化学股份有限公司Lodour 3630,苯乙烯-丙烯腈固含量约30%。
佳化化学股份有限公司Lodour 3645,苯乙烯-丙烯腈固含量约42%。
表面活性剂
反应型胺类催化剂
赢创特种化学(上海)有限公司Dabco NE300
赢创特种化学(上海)有限公司Dabco NE1082
有机金属类催化剂
赢创特种化学(上海)有限公司Kosmos 29,辛酸亚锡,有机锡类催化剂
甲苯二异氰酸酯
万华化学集团股份有限公司TDI 80/20
实施例1
使用连续式自动发泡剂(YY-01,扬宇机械),将各原料分别单独存放在密闭储罐或半开放式储罐且控制料温在一定温度,通过计量泵按表1a所示配方比例将各原料同时抽入带混合室和锯齿状搅拌棒的搅拌机头,除此之外还需要往混合室注入一定量的干燥空气,在设定好的混合室压力、搅拌棒转速、搅拌时间的条件下混合好物料,从混合机头出来的物料经由金属溢流槽或摆头装置流出,均匀分布在铺好底纸和侧纸的移动传送带上,物料沿着倾斜的跌落板向下流动且向上发泡,并按照一定的传送带速度向前移动,泡沫移动到跌落板装置后0.5-2.0米处达到最高点且上表面呈水平状态,经过加热温度为60℃,长度为8米的烘道后,连续状海绵被切断成一定长度的块状,块状海绵放入室内常温仓库继续熟化,然后裁切,裁切之后的半成品使用双辊破孔机进行机械碾压破孔,最终得到具有乳胶类似物性的低气味聚氨酯仿乳胶海绵制品。发泡过程中工艺参数如表1b所示。
表1a
表1b
| 工艺参数 | 数值 |
| 原料温度(℃) | 22 |
| 搅拌机头注气量(ml/min) | 50 |
| 搅拌机头压力(bars) | 1.0 |
| 搅拌机头转速(rpm) | 4000 |
| 搅拌时间(secs) | 2.0 |
| 传送带速度(m/min) | 3.5 |
| 海绵切断长度(m) | 3 |
| 海绵熟化时间(hrs) | 24 |
实施例2
制备方法同实施例1,不同之处在于往混合室注入的气体为氮气,其他原料种类、数量和工艺参数有所调整,具体的原料和工艺参数如表2a和表2b所示。
表2a
表2b
实施例3
制备方法同实施例1,不同之处在于原料种类、数量和工艺参数有所调整,具体的原料和工艺参数如表3a和表3b所示。
表3a
表3b
| 工艺参数 | 数值 |
| 原料温度(℃) | 25 |
| 搅拌机头注气量(ml/min) | 200 |
| 搅拌机头压力(bars) | 2 |
| 搅拌机头转速(rpm) | 5000 |
| 搅拌时间(secs) | 6.0 |
| 传送带速度(m/min) | 5 |
| 海绵切断长度(m) | 10 |
| 海绵熟化时间(hrs) | 40 |
实施例4
将20℃的原料伯羟基聚醚、聚合物聚醚、交联剂、水、表面活性剂、催化剂、甲苯二异氰酸酯和助剂同时混合,并向混合物中通入干燥的空气,将原料进行搅拌混合,搅拌压力为1.5bars,搅拌速度为4700rpm/min,搅拌时间为5s,干燥空气的通入速度为150ml/min,并同时进行发泡反应,然后熟化48h,碾压破孔,得到产品。原料种类和数量如表4a所示。
表4a
实施例5
将25℃的原料伯羟基聚醚、聚合物聚醚、交联剂、水、表面活性剂、催化剂、甲苯二异氰酸酯和助剂同时混合,并向混合物中通入干燥的空气,将原料进行搅拌混合,搅拌压力为1.5bars,搅拌速度为4500rpm/min,搅拌时间为4s,干燥空气的通入速度为100ml/min,并同时进行发泡反应,然后熟化30h,碾压破孔,得到产品。原料种类和数量如表5a所示。
表5a
对比例1
与实施例1相同,不同之处在于,将伯羟基聚醚替换为佳化化学F3020,分子量3000,环氧乙烷含量为15%,伯羟基比例为70%。
对比例2
与实施例1相同,不同之处在于,将伯羟基聚醚替换为佳化化学F3500M,分子量5000,环氧乙烷含量为80%,伯羟基比例为85%。
对比例3
与实施例1相同,不同之处在于,将聚合物聚醚替换为佳化化学PP2045B,基础聚醚为普通3000分子量的非高活性聚醚,固含量为45%。
对比例4
与实施例1相同,不同之处在于,NCO反应指数为1.20。
对比例5
与实施例1相同,不同之处在于,不使用交联剂。
实验例
本发明实验例涉及到的乳胶棉样品来自市场上常规在售的产品,且用于物性分析所采用的测试仪器、检测标准和检测项目均和本申请实施例和对比例所制备的聚氨酯海绵材料保持一致。
本发明实验例涉及的检测项目共11项,涵盖了基本物性(1密度)、物理机械性能(2表面硬度、3拉伸强度、4撕裂强度)、支撑承载性(525%IFD、6支撑因子、7落球回弹)、耐久性(8永久压缩变形)以及舒适性(9透气性、10气味、11手感)。
其中,海绵密度、拉伸强度、撕裂轻度、25%IFD、支撑因子、落球回弹、压缩变定、透气性的测试方法参照ASTM D3574中的相关规定。
表面硬度使用AskerF硬度计进行测定。
气味性能参照VDA270进行测试。
本发明实验例涉及的25%IFD(Indentation Force Deflection Test压陷应力应变测试)检测项目是指方块状海绵样品在试验机压头的作用下产生25%应变的所对应的应力值。用于评估聚氨酯海绵在不同变形的情况下对施加压力物体的支撑性。
本发明实验例涉及的支撑因子(Support Factor)也叫舒适因子(Sag Factor),是65%IFD与25%IFD比值,数值越高代表海绵的承载支撑性越好,由此带来的使用舒适度体验也越高。
本发明实验例涉及的气味测试项目采用汽车行业对聚氨酯海绵制品的评价标准VDA270进行测试评估,评分等级分别对应如下:
1分,难以感觉
2分,轻微但不难闻的气味
3份,明显的气味,但不难闻
4分,难闻的气味
5份,非常难闻
6分,无法忍受的气味
实施例和对比例所提供的聚氨酯海绵的性能参数如表6所示。
表6
通过实施例1-5可以得出,采用发明所述的制造工艺制得的聚氨酯仿乳胶海绵,相比较于乳胶海绵产品而言,可以生产出的产品密度更低,且聚氨酯海绵制品的物理机械性能(拉伸强度、撕裂强度)、耐久使用性能(压缩变定性能)以及透气性能更优越,体现海绵支撑特性的25%IFD、落球回弹以及支撑因子均落在乳胶产品的特性区间范围内,除此之外,聚氨酯海绵的手感和气味特性也和乳胶棉基本接近。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (11)
1.一种用于制备聚氨酯仿乳胶海绵的组合物,其特征在于,包括如下重量份的原料:
伯羟基聚醚70-90份;
聚合物聚醚10-30份;
交联剂0.5-2.5份;
甲苯二异氰酸酯20-30份;
其中,NCO反应指数为0.8-1.05,所述伯羟基聚醚为PO/EO共聚醚多元醇,所述伯羟基聚醚中环氧乙烷质量含量为10-20%,伯羟基比例为70-85%,重均分子量为4500-7500;所述聚合物聚醚为苯乙烯-丙烯腈聚合物接枝改性的伯羟基聚醚,且苯乙烯-丙烯腈聚合物在聚合物聚醚中的含量为20-45%。
2.根据权利要求1所述的用于制备聚氨酯仿乳胶海绵的组合物,其特征在于,所述甲苯二异氰酸酯为80wt%的2,4-甲苯二异氰酸酯和20wt%的2,6-甲苯二异氰酸酯的混合物。
3.根据权利要求1或2所述的用于制备聚氨酯仿乳胶海绵的组合物,其特征在于,所述交联剂为两官能度或三官能度的醇和/或醇胺。
4.根据权利要求1-3中任一项所述的用于制备聚氨酯仿乳胶海绵的组合物,其特征在于,所述交联剂为乙二醇、二丙二醇、1,4-丁二醇、甘油、二乙醇胺和三乙醇胺中的一种或几种。
5.一种聚氨酯仿乳胶海绵,其特征在于,包括权利要求1-4中任一项所述的组合物,以及
水1.4-2.3份;
表面活性剂0.5-1.5份;
催化剂0.12-1.1份;
助剂0-4份。
6.根据权利要求5所述的聚氨酯仿乳胶海绵,其特征在于,所述表面活性剂为聚醚改性聚硅氧烷。
7.根据权利要求5所述的聚氨酯仿乳胶海绵,其特征在于,所述催化剂为胺类催化剂和有机金属类催化剂的混合物。
8.根据权利要求7所述的聚氨酯仿乳胶海绵,其特征在于,所述胺类催化剂为含端羟基或端氨基的叔胺、苄胺和/或吗啉类催化剂,所述有机金属类催化剂为机金属锡类、有机铋类和/或有机锌类催化剂。
9.根据权利要求5-8中任一项所述的聚氨酯仿乳胶海绵,其特征在于,所述助剂为阻燃剂、亲水剂、色浆和/或抗菌剂。
10.权利要求5-9中任一项所述的聚氨酯仿乳胶海绵的制备方法,其特征在于,将原料伯羟基聚醚、聚合物聚醚、交联剂、水、表面活性剂、催化剂、甲苯二异氰酸酯和助剂同时混合,并向混合物中通入干燥的空气或惰性气体,将原料进行搅拌混合,并同时进行发泡反应,然后熟化,碾压破孔,得到产品。
11.根据权利要求10所述的聚氨酯仿乳胶海绵的制备方法,其特征在于,搅拌混合时压力为1.0-2.0bars、搅拌速度为4000-5000rpm/min,搅拌时间为2-6s,干燥的空气或惰性气体的通入速度为50-200ml/min。
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