CN110078967B - 仿真石材的半硬质聚氨酯材料及该仿真石材的制备方法 - Google Patents

仿真石材的半硬质聚氨酯材料及该仿真石材的制备方法 Download PDF

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CN110078967B
CN110078967B CN201910360365.8A CN201910360365A CN110078967B CN 110078967 B CN110078967 B CN 110078967B CN 201910360365 A CN201910360365 A CN 201910360365A CN 110078967 B CN110078967 B CN 110078967B
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王林生
黄海军
刘洋宏
陈亭
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Chongqing Odeon Industry Co.,Ltd.
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Abstract

为解决现有仿真石材存在的不能弯曲，无法对弧形、球形等特殊形状的建筑物进行安装等；对于转角的两个面，必须将仿真石材切割后，再进行安装，费事费力等问题，本发明提出一种仿真石材的半硬质聚氨酯材料由A组分和B组分组成，A组分由聚醚/聚酯多元醇、稀释剂、交联剂、催化剂、表面活性剂和发泡剂组成；B组分为多亚甲基多苯基多异氰酸酯或改性MDI中的一种或多种组成；A、B组分的质量比为1：(0.7‑0.8)。本发明还包括半硬质聚氨酯材料制备仿真石材的方法，本发明的仿真石材韧性好，硬度好，综合指标优异，可以进行U弯折后回复，对施工平面度的要求进一步降低，可以与墙面紧致贴合。

Description

仿真石材的半硬质聚氨酯材料及该仿真石材的制备方法
技术领域
本发明涉及聚氨酯材料技术领域，尤其涉及一种仿真石材的半硬质聚氨酯材料及该仿真石材的制备方法。
背景技术
石材是一种美观又耐用的装修材料，其不可复制的天然纹理及色彩变化，有种回归大自然的感觉，极具装饰效果。石材装饰如使用湿贴法施工，容易引起石材墙泛碱、变色、空鼓、脱落等；如使用干挂施工若防锈处理不到位，则容易造成龙骨生锈，进而发生石材脱落；石材长期处于室外，容易受到酸雨等腐蚀后，出现风化、褪色等质量问题，天然石材的原有孔隙及裂缝中的水分极易在寒暑变化及日夜温差条件下热胀冷缩，从而造成石材开裂。
仿真石材不仅具有天然石材般的仿真效果，更有富有创造力的外形和色彩，使用性能优异的高分子材料环保泡沫材料，仿真石材的重量只有不天然石材的1/10，兼具质轻、保温、防腐等功能，符合国家的节能环保要求，而且安装方便快捷，中国专利号为CN200610046396，以PVC等材料仿形外壳，然后向型腔浇注聚氨酯形成仿石产品，虽然具备专业化大批量生产条件，现场安装简单、方便、快捷等，但其仿石纹理不能弯曲，只能在平面上进行安装施工。
中国专利号为CN101077926 B描述了一种聚氨酯做成泡沫体，可以减轻聚氨酯仿真石材的重量，保温隔热性能好，化学稳定性好的仿真石材，其产品的规格、外观和色彩可以任意变化，石纹仿真度高，但其同样不能弯曲，对施工平面度仍有较高要求。
随着建筑业的不断发展，建筑物设计越趋复杂特异，对于弧形、圆柱、球形等特殊形状的建筑物来说，现有仿真石材由于不能弯曲，无法进行安装；对于转角的两个面，必须将仿真石材切割后，再进行安装，费事费力，大大限制了仿真石材的应用。
可见现有仿真石材存在着不能弯曲，无法对弧形、圆柱、球形等特殊形状的建筑物进行安装；对于转角的两个面，必须将仿真石材切割后，再进行安装，费事费力等问题。
发明内容
为解决现有仿真石材存在的不能弯曲，无法对弧形、球形等特殊形状的建筑物进行安装等；对于转角的两个面，必须将仿真石材切割后，再进行安装，费事费力等问题，本发明提出一种仿真石材的半硬质聚氨酯材料及该仿真石材的制备方法。
本发明一种仿真石材的半硬质聚氨酯材料由A组分和B组分组成，所述A组分由以下质量份的各物质组成：
Figure BDA0002046670140000022
所述B组分为多亚甲基多苯基多异氰酸酯或改性MDI中的一种或多种组成；所述A、B组分的质量比为1：(0.7-0.8)。
进一步的，所述A组分由以下质量份的各物质组成：
Figure BDA0002046670140000021
进一步的，所述A组分中聚醚/聚酯多元醇由聚醚多元醇1和聚醚多元醇2、聚醚多元醇3、聚酯多元醇中的一种或多种复配而成，其中聚醚多元醇1为必选聚醚多元醇；
其中，所述聚醚多元醇1以多元胺和/或多元醇为起始剂，以环氧丙烷为聚合单体，环氧乙烷封端聚合而成，环氧乙烷的质量分数为5-25％，以环氧乙烷和环氧丙烷的总质量为基准计算，平均官能度为2-4，数均分子量为3000-6000，所述起始剂包含甘油、三羟甲基丙烷、三乙醇胺、季戊四醇、二乙烯三胺和山梨醇中的一种或多种；
其中，所述聚醚多元醇2，以聚醚多元醇为基础，加丙烯腈、苯乙烯等及引发剂，在氮气保护下进行自由基接枝聚合而成；平均官能度为2-4，数均分子量为4000-8000，所述基础聚醚多元醇为环氧丙烷和环氧乙烷共聚醚；
其中，所述聚醚多元醇3，以多元醇为起始剂，以环氧丙烷为聚合单体，平均官能度为2-4，数均分子量为300-1000，所述起始剂由乙二醇、丙二醇、甘油、三羟甲基丙烷和季戊四醇中的一种或多种组成；
其中，所述聚酯多元醇，以二元羧酸与二元醇或加入少量三元醇为原料合成的聚酯多元醇。
进一步的，所述聚醚多元醇1环氧乙烷的质量分数为10-20％，以环氧乙烷和环氧丙烷的总质量为基准计算，平均官能度为3-4，数均分子量为4500-6000；所述起始剂由甘油、三羟甲基丙烷和三乙醇胺中的一种或多种组成；
所述聚醚多元醇2，平均官能度为3-4，数均分子量为5000-7000；
所述聚醚多元醇3，平均官能度3，数均分子量为300-500，所述起始剂为乙二醇、丙二醇、甘油和三羟甲基丙烷中的一种或多种组成。
进一步的，所述稀释剂为低粘度的碳酸酯类、磷酸酯类、卤代磷酸酯类中的一种或几种复配而成，其粘度为1-50mpa﹒s。
进一步的，所述交联剂为二醇、三醇、四醇、醇胺、二胺中的一种或多种含有2个及其以上可与异氰酸酯反应的官能团的化合物组成。
进一步的，所述催化剂为催化剂1、催化剂2、催化剂3和催化剂4中的一种或多种组成；
其中，所述催化剂1为催发型催化剂，包含催发型胺类催化剂，所述催发型胺类催化剂可以包含或不包含氧原子；
其中，所述催化剂2为凝胶型催化剂，包括凝胶型胺类催化剂、脒、有机金属化合物或其组合；
其中，所述催化剂3为平衡型催化剂，是包含环状叔胺或长链胺；
其中，所述催化剂4为三聚型催化剂，包含氮族元素化合物、有机金属化合物等作为脂肪族及芳香族异氰酸酯的三聚反应催化剂。
进一步的，所述表面活性剂包含硅氧烷类表面活性剂和/或含氟类表面活性剂；
进一步的，所述表面活性剂为聚硅氧烷-聚氧化烯烃类共聚物，硅含量为8-12％，接枝聚醚多元醇碳链长度为40-60，制备接枝聚醚多元醇的环氧丙烷和环氧乙烷摩尔比为1:1.5-4。
进一步的，所述发泡剂为低沸点烃类、水、CO2中的一种或几种的复配物。
本发明还包括上述半硬质聚氨酯材料制备仿真石材的方法，该方法包括以下步骤：
S1、在模具上喷涂隔离剂；
S2、待隔离剂喷涂2-3min后，喷涂模内漆；
S3、将半硬质聚氨酯材料按比例混合均匀，浇注于喷好模内漆的模具型腔内，盖上模具型腔盖板，模具锁模力2.5-3.5公斤力/cm2保持5-15分钟；
S4、打开模具，取出产品，即得到本发明半硬质聚氨酯材料制备的仿真石材。
本发明通过对聚氨酯配方的优化，有效解决了现有仿真石材不能弯曲，无法对弧形、球形等特殊形状的建筑物进行安装等问题。
本发明对半硬质聚氨酯材料进行了深入研究，本发明中催化剂1为催发型催化剂包含催发型胺类催化剂，所述催发型胺类催化剂可以包含或不包含氧原子，其实例包括双(二甲基氨基乙基)醚(A1)、N,N-二甲基乙醇胺(DMEA)、N,N-二甲基环己胺、五甲基二亚乙基三胺、N,N-二甲基异丙基丙二胺、三乙胺、三丁基胺、N,N-二甲基氨基丙基胺、二甲基乙醇胺、N,N,N’,N’-四甲基乙二胺、N,N,N’-三甲基-N’-羟乙基双氨乙基醚中的一种或多种。其他可从商业上购买的催发型催化剂实例还包括万华化学的KC121等。
催化剂2为凝胶型催化剂的例子包括但不限于凝胶型胺类催化剂、脒、有机金属化合物或其组合。所述凝胶型胺类催化剂的实例包括但不限于三亚乙基二胺(A33)、N,N-二甲基-N',N'-二(2-羟丙基)-1,3-丙二胺等。所述脒的实例包括但不限于1,8-二氮杂二环[5.4.0]十一碳-7-烯和2,3-二甲基-3,4,5,6-四氢嘧啶、及它们的盐。所述有机金属化合物可包括有机锡化合物，如二月桂酸二丁基锡、辛酸亚锡、二乙酸二丁基锡、二乙酸二辛基锡和马来酸二丁基锡等。有机钾化合物，如醋酸钾、辛酸钾等。也可选择有机羧酸的铋盐。其他合适的凝胶型催化剂实例如2,4,6-三(二甲氨基甲基)苯酚。其他可从商业上购买的凝胶型催化剂还包括万华化学的KC-100、KC101等。
催化剂3为平衡型催化剂的实例是包含环状叔胺或长链胺，如二甲基苄胺、N-甲基吗啉、N-环己基吗啉、N-乙基吗啉、N,N,N’,N’-四甲基-1,4-丁二胺、N,N,N’,N’-四甲基-1,6-己二胺、二(二甲基氨基丙基)脲、二甲基哌嗪、二甲基环己胺、1,2-二甲基-咪唑、1-氮杂-双环[3.3.0]辛烷等，这类催化剂可任选地单独或组合使用。
本发明所述的平衡型催化剂的另一类别是链烷醇胺化合物，如三异丙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、二甲基乙醇胺等，这类催化剂可任选地单独或组合使用。
催化剂4为三聚型催化剂包含氮族元素化合物、有机金属化合物等作为脂肪族及芳香族异氰酸酯的三聚反应催化剂，如2-羟基-N,N,N-三甲基-1-丙胺的甲酸盐、N,N',N”-三(二甲氨基丙基)-六氢化三嗪、2,4,6-三(二甲氨基甲基)苯酚是常用的叔胺类三聚催化剂。
所述催发型催化剂包含催发型胺类催化剂，优选包含双(二甲基氨基乙基)醚、N,N-二甲基乙醇胺、N,N-二甲基环己胺、五甲基二亚乙基三胺、N,N-二甲基异丙基丙二胺、三乙胺、三丁基胺、N,N-二甲基氨基丙基胺、二甲基乙醇胺、N,N,N’,N’-四甲基乙二胺、N,N,N’-三甲基-N’-羟乙基双氨乙基醚和万华化学公司的KC121中的一种或多种；更优选双(二甲氨基乙基)醚、N,N-二甲基乙醇胺、N,N-二甲基环己胺、五甲基二亚乙基三胺、N,N-二甲基异丙基丙二胺、N,N,N’-三甲基-N’-羟乙基双氨乙基醚和万华化学公司的KC121中的一种或多种；
所述凝胶型催化剂包含凝胶型胺类催化剂、脒、有机金属化合物中的一种或多种，优选包含三亚乙基二胺、1,8-二氮杂二环[5.4.0]十一碳-7-烯、2,3-二甲基-3,4,5,6-四氢嘧啶、有机锡化合物、有机羧酸的铋盐、2,4,6-三(二甲氨基甲基)苯酚、N,N-二甲基-N',N'-二(2-羟丙基)-1,3-丙二胺、万华化学公司的KC-100、KC101中的一种或多种；更优选2,4,6-三(二甲氨基甲基)苯酚、三亚乙基二胺、二月桂酸二丁基锡、辛酸亚锡、二乙酸二丁基锡、万华化学公司的KC-100和KC101的一种或多种。
所述催化剂4为三聚催化剂，优选2-羟基-N,N,N-三甲基-1-丙胺的甲酸盐、N,N',N”-三(二甲氨基丙基)-六氢化三嗪。
本发明通过对半硬质聚氨酯材料配方的改进、创新，制备出半硬质聚氨酯材料的仿真石材，该仿真石材韧性好，硬度好，综合指标优异，并没有因为韧性的提高而牺牲硬度指标。本发明产品的规格、外观和色彩可以任意变化，仿石纹理仿真度高，质感好，化学稳定性好的仿真石材。本发明产品韧性好，可以进行U弯折后回复，对施工平面度的要求进一步降低，可以与墙面紧致贴合。
本发明的另一个目的是提供一种半硬质聚氨酯仿真石材的制备方法，其过程为在仿真模纹理图案面上喷涂隔离剂/脱模剂，然后在仿真模型腔的内表面喷涂彩色颜料/油漆，用聚氨酯泡沫材料填充在仿真模型腔中形成半硬质仿真石材。仿真模型腔的内表面的颜料通过粘合与发泡压力作用，渗进仿真石材，颜料融合在仿真石材的表面形成彩色艳丽的表面层。由于隔离剂/脱模剂的存在，固化后的仿真石材与仿真模可以轻松分离，并不会因为立体纹理图案而脱模困难。通过本发明产品，化学稳定性和尺寸稳定性好，耐侯性佳。另外本发明产品仅需铆钉安装，无需粘接剂和水泥砂浆，安装方便快捷，并且具有天然石材的质感，用户满意度较高。
附图说明
附图1为本发明半硬质聚氨酯仿真石材图。
附图2为本发明半硬质聚氨酯仿真石材90°弯曲状态图。
附图3为本发明半硬质聚氨酯仿真石材U型弯曲状态图。
附图4为市售聚氨酯仿真石材图。
附图5为市售聚氨酯仿真石材弯曲状态图。
附图6为市售聚氨酯仿真石材90°弯曲状态图。
下面结合附图和具体实施例对本发明半硬质聚氨酯仿真石材作进一步的说明。
具体实施方式
本发明全文各组分中所指的化学名称、结构式、或以本领域技术人员熟知的技术参数作出限制的化学物质，均表示对本发明反应体系起作用的有效成分，也表示为所述组分的全部成分或主要成分，而除此之外包含的少量杂质或溶剂等，是本领域中常见的情况，并不影响本发明的反应体系和技术方案的实施。本发明未做说明的内容，如组分中的杂质、少量溶剂、制备方法等，均可以采用本领域技术人员熟知的内容进行解释和说明。
制备半硬质聚氨酯材料：
仿真石材半硬质聚氨酯材料部分由A组分和B组分组成，其中A组分的成分为聚醚多元醇、聚酯多元醇、稀释剂、表面活性剂、发泡剂、催化剂，各成分的重量百分比如下表：
Figure BDA0002046670140000071
Figure BDA0002046670140000081
Figure BDA0002046670140000082
Figure BDA0002046670140000091
Figure BDA0002046670140000092
将上述原料按从上至下的顺序加入有搅拌的料桶中混合均匀30-120分钟形成本专利所述聚氨酯材料的A组分，B组分为多亚甲基多苯基多异氰酸酯或多亚甲基多苯基多异氰酸酯与改性MDI掺混使用。A、B组分的重量比为1：0.7-0.8，将A、B组分使用设备或人工按比例混合均匀后即得聚氨酯发泡材料，该混合物在10-30秒内开始发泡，1-3分钟内停止生长，聚氨酯材料在模具的保压时间为5-15分钟。
本发明还包括上述半硬质聚氨酯材料制备仿真石材的方法，该方法包括以下步骤：
S1、在模具上喷涂隔离剂；
S2、待隔离剂喷涂2分钟内，喷涂模内漆；
S3、将半硬质聚氨酯材料按比例混合均匀，浇注于喷好真石漆的模具型腔内，盖上模具型腔盖板，在模具锁模力2.5-3.5公斤力/cm2保持5-15分钟；；
S4、打开模具，取出产品，即得到本发明半硬质聚氨酯材料制备的仿真石材。下表为实施例1-18生产出的仿真石材和市售产品检测指标：
Figure BDA0002046670140000101
Figure BDA0002046670140000102
Figure BDA0002046670140000111
Figure BDA0002046670140000112
Figure BDA0002046670140000121
由检测结果和附图可知，本本发明的仿真石材韧性好，硬度好，综合指标优异，并没有因为韧性的提高而牺牲硬度指标。化学稳定性和尺寸稳定性好，耐侯性佳。本发明中有部分实施例存在外观略微胀气和轻微收缩，但是不影响产品的最终成品，而市售产品是胀气，空泡缺陷较多，所以，本发明也大大优于现有的同类产品。
本发明产品的规格、外观和色彩可以任意变化，仿石纹理仿真度高，质感好，化学稳定性好的仿真石材。本发明产品韧性好，可以进行U弯折后回复，对施工平面度的要求进一步降低，可以与墙面紧致贴合。另外本发明产品仅需铆钉安装，无需粘接剂和水泥砂浆，安装方便快捷，并且具有天然石材的质感，具有广阔的市场前景。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (2)

1.一种仿真石材的半硬质聚氨酯材料，所述半硬质聚氨酯材料由A 组分和B 组分组成，其特征在于，所述A组分由以下质量份的各物质组成：
聚醚多元醇1 65
聚醚多元醇2 5
聚醚多元醇3 5
聚酯多元醇 25
亚烷基碳酸酯稀释剂 5
TCPP稀释剂 15
乙二醇 5
二甘醇 5
双（二甲基氨基乙基）醚 0.2
三亚乙基二胺 0.5
催化剂C225 0.1
催化剂TMR-2 0.1
聚硅氧烷-聚氧化烯烃类共聚物 1.0
H2O 0.8；
所述B组分由以下质量份的各物质组成：
多亚甲基多苯基多异氰酸酯 80
改性MDI 19.52；
所述A、B组分的质量比为1：0.75；
其中，所述聚醚多元醇1以多元胺和/或多元醇为起始剂，以环氧丙烷为聚合单体，环氧乙烷封端聚合而成，环氧乙烷的质量分数为5-25%，以环氧乙烷和环氧丙烷的总质量为基准计算，平均官能度为2-4，数均分子量为3000-6000，所述起始剂包含甘油、三羟甲基丙烷、三乙醇胺、季戊四醇、二乙烯三胺和山梨醇中的一种或多种；
其中，所述聚醚多元醇2，以聚醚多元醇为基础，加丙烯腈或苯乙烯引发剂，在氮气保护下进行自由基接枝聚合而成；平均官能度为2-4，数均分子量为4000-8000，所述基础聚醚多元醇为环氧丙烷和环氧乙烷共聚醚；
其中，所述聚醚多元醇3，以多元醇为起始剂，以环氧丙烷为聚合单体，平均官能度为2-4，数均分子量为300-1000，所述起始剂由乙二醇、丙二醇、甘油、三羟甲基丙烷和季戊四醇中的一种或多种组成；
其中，所述聚酯多元醇，以二元羧酸与二元醇或加入少量三元醇为原料合成的聚酯多元醇。
2.根据权利要求1所述的半硬质聚氨酯材料制备仿真石材的方法，该方法包括以下步骤：
S1、在模具上喷涂隔离剂；
S2、待隔离剂喷涂2-3min后，喷涂模内漆；
S3、 将半硬质聚氨酯材料按比例混合均匀，浇注于喷好模内漆的模具型腔内，盖上模具型腔盖板，模具锁模力2.5-3.5公斤力/cm2保持5-15分钟；
S4、打开模具，取出产品，即得半硬质聚氨酯材料制备的仿真石材。
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CN110437406B (zh) * 2019-08-30 2021-09-03 惠彩材料科技(苏州)有限公司 一种低密度半硬质聚氨酯材料及制备方法和应用
CN111087570B (zh) * 2019-12-25 2022-07-12 万华化学（北京）有限公司 聚氨酯泡沫及其制备方法、聚氨酯泡沫夹层部件及其制备方法和用途
CN111116854B (zh) * 2019-12-25 2022-07-15 万华化学（北京）有限公司 半硬质聚氨酯泡沫及其制备方法、夹层部件及其制备方法和用途
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CN111620996A (zh) * 2020-06-19 2020-09-04 长春富维安道拓汽车饰件系统有限公司 一种低气味快速脱模聚氨酯半硬质泡沫

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