CN111138621A - 一种聚氨酯树脂及铺装复合材料 - Google Patents

一种聚氨酯树脂及铺装复合材料 Download PDF

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CN111138621A
CN111138621A CN201911367672.5A CN201911367672A CN111138621A CN 111138621 A CN111138621 A CN 111138621A CN 201911367672 A CN201911367672 A CN 201911367672A CN 111138621 A CN111138621 A CN 111138621A
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polyurethane resin
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马宝光
林滨
蔡倩莹
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Zhuhai Guanglin New Material Technology Co Ltd
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Abstract

本发明提供一种聚氨酯树脂及铺装复合材料，本发明提供的聚氨酯树脂，包括A组分和B组分，按重量份计，所述A组分包括10‑90份聚醚多元醇、10‑90份聚酯多元醇和助剂0.1‑50份，所述B组分包括50‑100份异氰酸酯和0.1‑80份吸附性无机填料。本发明提供的聚氨酯树脂及铺装复合材料更加安全环保。

Description

一种聚氨酯树脂及铺装复合材料
技术领域
本发明属于聚氨酯技术领域，具体涉及一种聚氨酯树脂及铺装复合材料。
背景技术
随着孩子上学越来越早，幼儿园办的越来越多，对于铺装材料需求量逐渐增大，要求也变得更严格。幼儿园或者早教机构一般接受的是2岁～12岁年龄阶段的小孩子。处于此年龄阶段的孩子们心智和身体都在发育，他们对这个世界和新鲜事物都处于好奇和探索的阶段，所以他们活泼好动，天真单纯可爱，爱玩耍是他们的天性，因此幼儿园教育机构无论是对师资，还是室内的安装都是有一定的要求，必须具有一定的安全性，让小朋友们健康成长，幼儿园对室内墙角的安装是有一定的要求的，必须要软化，防止小朋友撞伤，磕碰等。
目前，传统用于墙角、地面、墙面的材料不能达到环保标准，voc含量过高且挥发太慢，对处于相对密封环境的幼儿及老师造成持久性的损伤。
发明内容
针对现有技术的不足，本发明提供安全性较好的聚氨酯树脂及及铺装复合材料。
本发明提供一种聚氨酯树脂，包括A组分和B组分，按重量份计，所述A组分包括10-90份聚醚多元醇、10-90份聚酯多元醇和助剂0.1-50份，所述B组分包括50-100份异氰酸酯和0.1-80份吸附性无机填料。
优选地，所述吸附性无机填料为10-50份。
优选地，所述吸附性无机填料包括石墨烯、分子筛、蒙脱土、凹凸棒土和炭黑的一种或多种。
优选地，所述助剂包括0-0.2份阻聚剂、1-10份发泡剂、0.1-2份催化剂、0.5-10份交联剂、0.2-10份泡沫稳定剂和0.2-10份扩链剂。
优选地，所述聚醚多元醇分子量为300-7000，官能度为2-5，粘度为150-10000mPa*s。
优选地，所述聚酯多元醇羟基值为50-200mg/g KOH，酸值0.1-1mg/g KOH，粘度为100-3000mPa*s。
优选地，所述聚醚多元醇40-90份，所述聚酯多元醇20-70份，所述异氰酸酯70-100份。
优选地，所述吸附性无机填料为经过化学改性后的改性填料，所述改性填料含有0.2-5％的改性官能团，所述改性官能团包括有机硅、羟基或羧基官能团中的一种或多种。
优选地，所述聚醚多元醇为聚氧化丙烯二醇、聚醚三醇、聚醚四醇、聚四氢呋喃二醇、聚四氢呋喃-氧化丙烯共聚醚二醇中的一种或多种；
所述聚酯多元醇为己二酸系聚酯二醇、芳香族聚酯多元醇、二聚体聚酯二醇、端羟基聚丁二烯、聚己内酯多元醇、端羟基聚丁二烯-丙烯腈中的一种或多种；
所述异氰酸酯为六亚甲基二异氰酸酯、HDI缩二脲、HDI三聚体，异佛尔酮二异氰酸酯(IPDI)，IPDI三聚体，二环己基甲烷二异氰酸酯(HMDI)及其加成物，甲苯二异氰酸酯(TDI)及其加成物，二苯基甲烷二异氰酸酯(MDI)及其加成物，苯二亚甲基二异氰酸酯(XDI)及其加成物中的一种或多种。
本发明还提供一种铺装复合材料，从上到下依次包括有机硅层、聚氨酯层、橡胶层和塑料层。
优选地，所述有机硅层包括聚二甲基硅氧烷，环甲基硅氧烷，氨基硅氧烷，聚甲基苯基硅氧烷，聚醚聚硅氧烷共聚物的一种或多种组合物；
所述橡胶层为顺丁橡胶、天然橡胶、氯丁橡胶或丁腈橡胶的一种或多种组合物；
所述塑料层为聚氯乙烯、尼龙、聚苯乙烯、聚甲基丙烯酸甲酯、聚对苯二甲酸乙二醇酯的一种或多种组合物。
优选地，所述有机硅层厚度为0.1-10cm，所述聚氨酯层厚度为1-10cm，所述橡胶层厚度为1-10cm，所述塑料层厚度为1-50cm。
本发明提供的聚氨酯树脂及铺装复合材料更加安全环保。
附图说明
通过附图中所示的本发明优选实施例更具体说明，本发明上述及其它目的、特征和优势将变得更加清晰。在全部附图中相同的附图标记指示相同的部分，且并未刻意按实际尺寸等比例缩放绘制附图，重点在于示出本的主旨。
图1为本发明实施例提供的铺装复合材料结构示意图。
具体实施方式
下面结合具体实施例对本发明技术方案作进一步的详细描述，以使本领域的技术人员可以更好的理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
参考图1，本发明实施例提供一种聚氨酯树脂，包括A组分和B组分，按重量份计，A组分包括10-90份聚醚多元醇、10-90份聚酯多元醇和助剂0.1-50份，B组分包括50-100份异氰酸酯和0.1-80份吸附性无机填料。
本实施例的吸附性无机填料吸附能力强、比表面积大使聚氨酯在制备后，voc挥发到空气中被吸附能力强的无机填料所吸附，一周内voc浓度可达到国家标准，更加安全环保。
本发明实施例提供的聚氨酯树脂可用于制备幼儿园或早教中心铺装复合材料。例如防撞条、防撞海绵等产品，但并不局限于这两种产品。
在优选实施例中，吸附性无机填料为10-50份、5-25份或8-30份。
在优选实施例中，吸附性无机填料包括石墨烯、分子筛、蒙脱土、凹凸棒土和炭黑的一种或多种，这些材料具有较强的吸附能力，较大的比表面积，能较大程度的吸附voc，使voc排放浓度在较短的时间内达国家标准。同时选用这些材料作为吸附性无机填料，与聚氨酯树脂的其他配方配合相容性较好，制备得到的聚氨酯树脂各方面性能都较好。
在优选实施例中，吸附性无机填料为经过化学改性后的改性填料，改性填料含有0.2-5％的改性官能团，改性官能团包括有机硅、羟基或羧基官能团中的一种或多种。吸附性无机填料改性后增加无机填料与聚氨酯的共混性能，且提升无机填料对voc的吸附性能。
在优选实施例中，助剂包括0-0.2份阻聚剂、1-10份发泡剂、0.1-2份催化剂、0.5-10份交联剂、0.2-10份泡沫稳定剂和0.2-10份扩链剂。
在进一步优选实施例中，聚氨酯树脂，由A组分和B组分组成，按重量份计，A组分由10-90份聚醚多元醇、10-90份聚酯多元醇、0-0.2份阻聚剂、1-10份发泡剂、0.1-2份催化剂、0.5-10份交联剂、0.2-10份泡沫稳定剂和0.2-10份扩链剂组成，B组分由50-100份异氰酸酯和0.1-80份吸附性无机填料组成。
在优选实施例中，聚醚多元醇分子量为300-7000，官能度为2-5，粘度为150-10000mPa*s，能够较好的制备聚氨酯树脂。
在优选实施例中，聚酯多元醇羟基值为50-200mg/g KOH，酸值0.1-1mg/g KOH，粘度为100-3000mPa*s，能够较好的制备聚氨酯树脂。
在优选实施例中，聚醚多元醇40-90份，更优选聚醚多元醇45-80份。聚酯多元醇20-70份，更优选聚酯多元醇为25-60份。异氰酸酯70-100份，更优选异氰酸酯80-100份。
在优选实施例中，聚醚多元醇为聚氧化丙烯二醇、聚醚三醇、聚醚四醇、聚四氢呋喃二醇、聚四氢呋喃-氧化丙烯共聚醚二醇中的一种或多种。
在优选实施例中，聚酯多元醇为己二酸系聚酯二醇、芳香族聚酯多元醇、二聚体聚酯二醇、端羟基聚丁二烯、聚己内酯多元醇、端羟基聚丁二烯-丙烯腈中的一种或多种；
在优选实施例中，异氰酸酯为六亚甲基二异氰酸酯、HDI缩二脲、HDI三聚体，异佛尔酮二异氰酸酯(IPDI)，IPDI三聚体，二环己基甲烷二异氰酸酯(HMDI)及其加成物，甲苯二异氰酸酯(TDI)及其加成物，二苯基甲烷二异氰酸酯(MDI)及其加成物，苯二亚甲基二异氰酸酯(XDI)及其加成物中的一种或多种。
本实施例提供的聚氨酯树脂常温下其损耗模量(G”)与储能模量(G’)比值大于0.5。材料较为柔软，具有较好的防撞效果。
本实施例提供的聚氨酯树脂在放置1周后进行voc含量测试，24小时内，每10g聚氨酯挥发的总voc含量小于10μg，其中苯小于5μg，甲苯小于5μg，乙酸甲酯小于10μg。
本实施例提供的聚氨酯树脂在空气流速为0.01-0.1m/s环境中，苯浓度小于10μg/m3,甲苯浓度小于10μg/m3。
本发明实施例还提供一种聚氨酯树脂的制备方法，包括如下步骤：
(1)将A组分各组分在常温下以3000rpm混合；
(2)加入B组分继续搅拌；
(3)倒入预热至40-60℃的模具中，脱模后得到聚氨酯树脂。
在优选实施例中，倒入预热至46-60℃的模具中，脱模后得到聚氨酯树脂。
参考图1，本发明实施例还提供一种铺装复合材料，从上到下依次包括有机硅层4、聚氨酯层3、橡胶层2和塑料层1。
本实施例中聚氨酯层3由上述任一项实施例所指的聚氨酯树脂得到。聚氨酯层3能够起到吸收VOC气体的作用，使得材料更加安全环保。同时聚氨酯层3还用于提供一定的弹性，具有较好的防撞效果。橡胶层2用于更进一步提升材料整体的弹性，使得防撞效果更佳。塑料层1起到保护密封的作用，用于保护整个铺装复合材料，防止灰尘进入铺装复合材料内部，影响聚氨酯层3和橡胶层2的弹性。有机硅层4具有憎水基团，可实现防脏耐水的作用，避免水分进入铺装复合材料内部，影响聚氨酯层3和橡胶层2，使得铺装复合材料寿命下降。
在优选实施例中，有机硅包括聚二甲基硅氧烷，环甲基硅氧烷，氨基硅氧烷，聚甲基苯基硅氧烷，聚醚聚硅氧烷共聚物的一种或多种组合物，实现较好的防水耐脏效果。
在优选实施例中，有机硅常温下储能模量不大于1e7 Pa，且损耗角为0.1-1。材料较为柔软，具有较好的防撞效果。
在优选实施例中，橡胶层2为顺丁橡胶、天然橡胶、氯丁橡胶或丁腈橡胶的一种或多种组合物，能够提供较好的弹性。
在优选实施例中，塑料层1为聚氯乙烯、尼龙、聚苯乙烯、聚甲基丙烯酸甲酯、聚对苯二甲酸乙二醇酯的一种或多种组合物。
在优选实施例中，所述有机硅层4厚度为0.1-10cm，所述聚氨酯层3厚度为1-10cm，所述橡胶层2厚度为1-10cm，所述塑料层1厚度为1-50cm。合理设置各层之前的厚度，实现制备得到的铺装复合材料不但具有较好的弹性，较低的voc排放，还能具有较高的使用寿命。
本实施例提供的铺装复合材料可用于幼儿园、早教中心或者家中日常的铺装，能够起到防撞的效果，同时还具有较低的voc浓度。
为使本发明上述发明实施例的细节更利于本领域技术人员的理解和实施，以及突出本案的进步性效果，以下通过具体的实施例来对本案的上述内容进行举例说明。
实施例1
A组分包括50份聚氧化丙烯二醇、50份芳香族聚酯多元醇和二聚体聚酯二醇，0.2份对苯二酚，2份水，1份叔胺催化剂，3份甘油，3份有机硅表面活性剂，2份醇类扩链剂，B组分包括HDI缩二脲和IPDI共90份，纳米级凹凸棒土10份。把A组分各组分在常温下以5000rpm混合，加入B组分继续在3000rpm搅拌5min，倒入预热至50℃的模具中，30min后脱模，得到聚氨酯树脂。
实施例2
A组分包括70份聚醚三醇和聚醚四醇、30份端羟基聚丁二烯-丙烯腈，0.1份苯甲醛，2份氟氯烃，2份叔胺催化剂，5份乙二醇，5份有机硅表面活性剂，1份醇类扩链剂，B组分包括HMDI 90份，纳米级蒙脱土20份炭黑0.2份。把A组分各组分在常温下以3000rpm混合，加入B组分继续在3000rpm搅拌10min，倒入预热至50℃的模具中，10min后脱模，得到聚氨酯树脂。
对比例
与实施例1相比，对比例中B组分包括HDI缩二脲和IPDI共100份，不加入无机填料，其余配方和制备方法与实施例1相同。
将实施例1-2和对比例制备得到的聚氨酯树脂进行拉伸强度、硬度、弹性模量(G”)、储能模量(G’)和voc含量和挥发量测试。具体数据如表1所示。
表1
Figure BDA0002338865240000061
Figure BDA0002338865240000071
通过表1的数据可以看出，本实施例1-2制备得到的聚氨酯树脂放置一周后voc每10g聚氨酯树脂挥发量仅有8μg和8.1μg，对比例中未加入吸附性无机填料，放置一周后voc每10g聚氨酯树脂挥发量为106.2μg。可见本发明合理加入吸附性无机填料，以及加入合理的比例，以及和其他配方合理配合，实现得到的聚氨酯树脂具有较低的voc挥发量。
本实施例1-2制备得到的聚氨酯树脂在风速0.05m/s,200m3的早教场地实际使用时voc含量最多仅有0.81μg/m3，相比没有加入吸附性无机填料的聚氨酯树脂，voc含量低很多。可见本发明合理加入吸附性无机填料，以及加入合理的比例，以及和其他配方合理配合，实现得到的聚氨酯树脂具有较低的voc含量。
并且本实施例1-2制备的聚氨酯树脂依然能够具有较好的硬度，也能够将拉伸强度保持在较好的范围。
说明本发明配方合理，制备得到的聚氨酯树脂voc含量和voc挥发量较低，并且有用较高的硬度，还能保持抗拉强度不会有较大的降低。
以上仅为本发明的优选实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (10)

1.一种聚氨酯树脂，其特征在于，由A组分和B组分混合得到，按重量份计，所述A组分包括10-90份聚醚多元醇、10-90份聚酯多元醇和助剂0.1-50份，所述B组分包括50-100份异氰酸酯和0.1-80份吸附性无机填料。
2.如权利要求1所述的聚氨酯树脂，其特征在于，所述吸附性无机填料为10-50份。
3.如权利要求1所述的聚氨酯树脂，其特征在于，所述吸附性无机填料包括石墨烯、分子筛、蒙脱土、凹凸棒土和炭黑的一种或多种。
4.如权利要求1所述聚氨酯树脂，其特征在于，所述吸附性无机填料为经过化学改性后的改性填料，所述改性填料含有0.2-5％的改性官能团，所述改性官能团包括有机硅、羟基或羧基官能团中的一种或多种。
5.如权利要求1所述的聚氨酯树脂，其特征在于，所述助剂包括0-0.2份阻聚剂、1-10份发泡剂、0.1-2份催化剂、0.5-10份交联剂、0.2-10份泡沫稳定剂和0.2-10份扩链剂。
6.如权利要求1所述的聚氨酯树脂，其特征在于，所述聚醚多元醇分子量为300-7000，官能度为2-5，粘度为150-10000mPa*s；所述聚酯多元醇羟基值为50-200mg/g KOH，酸值0.1-1mg/g KOH，粘度为100-3000mPa*s。
7.如权利要求1所述的聚氨酯树脂，其特征在于，所述聚醚多元醇40-90份，所述聚酯多元醇20-70份，所述异氰酸酯70-100份。
8.一种铺装复合材料，其特征在于，从上到下依次包括有机硅层、如权利要求1-7任一项所述的聚氨酯层、橡胶层和塑料层。
9.如权利要求8所述的铺装复合材料，其特征在于，所述有机硅层包括聚二甲基硅氧烷，环甲基硅氧烷，氨基硅氧烷，聚甲基苯基硅氧烷，聚醚聚硅氧烷共聚物的一种或多种组合物；
所述橡胶层为顺丁橡胶、天然橡胶、氯丁橡胶或丁腈橡胶的一种或多种组合物；
所述塑料层为聚氯乙烯、尼龙、聚苯乙烯、聚甲基丙烯酸甲酯、聚对苯二甲酸乙二醇酯的一种或多种组合物。
10.如权利要求8所述的铺装复合材料，其特征在于，所述有机硅层厚度为0.1-10cm，所述聚氨酯层厚度为1-10cm，所述橡胶层厚度为1-10cm，所述塑料层厚度为1-50cm。
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CN106739346A (zh) * 2017-01-17 2017-05-31 广东工业大学 一种聚氨酯铺地材料
CN108299621A (zh) * 2018-02-09 2018-07-20 山东赢方体育产业有限公司 一种环保型塑胶跑道及其制备方法
CN110078884A (zh) * 2019-04-19 2019-08-02 广东大盈新材料科技有限公司 一种无机纳米材料改性聚氨酯树脂及其制备方法

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CN114249934A (zh) * 2020-09-24 2022-03-29 重庆市智翔铺道技术工程有限公司 钢结构人行天桥铺装材料及其制备方法
CN114249934B (zh) * 2020-09-24 2023-10-20 重庆市智翔铺道技术工程有限公司 钢结构人行天桥铺装材料及其制备方法
GB2600100A (en) * 2020-10-16 2022-04-27 Resin By Installers Ltd Resin installed surfacing

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