CN110317563B - 一种复合聚酯热熔胶、制备方法及抗冲刷土工布的制备方法 - Google Patents

一种复合聚酯热熔胶、制备方法及抗冲刷土工布的制备方法 Download PDF

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CN110317563B
CN110317563B CN201910611143.9A CN201910611143A CN110317563B CN 110317563 B CN110317563 B CN 110317563B CN 201910611143 A CN201910611143 A CN 201910611143A CN 110317563 B CN110317563 B CN 110317563B
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China
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hot melt
melt adhesive
polyester hot
composite
preparation
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CN110317563A (zh
Inventor
于沭
陈祖煜
张茂省
薛强
李炎隆
司政
李鹏
边京红
郝建伟
周嘉伟
岳凡
张茵琪
晁华怡
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China Institute of Water Resources and Hydropower Research
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China Institute of Water Resources and Hydropower Research
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Priority to CN201910611143.9A priority Critical patent/CN110317563B/zh
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Priority to US17/258,163 priority patent/US20220348804A1/en
Priority to PCT/CN2020/100296 priority patent/WO2021004410A1/zh
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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Civil Engineering (AREA)
  • Textile Engineering (AREA)
  • Mining & Mineral Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Soil Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Paleontology (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Architecture (AREA)
  • Polyesters Or Polycarbonates (AREA)
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Abstract

本发明公开了一种复合聚酯热熔胶、制备方法及抗冲刷土工布的制备方法,属于聚酯类热熔胶制备技术领域。其复合聚酯热熔胶的制备方法,其包括以下步骤:将二元酸和二元醇在钛/钴复合催化剂作用下,在氮气保护下进行酯化反应,然后加入稳定剂进行缩聚反应,得到聚酯热熔胶再加入聚甲基丙烯酸甲酯微球混合搅拌得到复合聚酯热熔胶。将得到的复合聚酯热熔胶粘合聚对苯二甲酸乙二醇脂编织布和聚丙烯土工布可得到抗冲刷土工布。本发明的复合聚酯热熔胶其粘结强度高、耐冲击性好,制备的抗冲刷土工布具有抗冲刷强度高、保土性能好、防护能力强、使用寿命长的优点。

Description

一种复合聚酯热熔胶、制备方法及抗冲刷土工布的制备方法
技术领域
本发明涉及聚酯类热熔胶制备技术领域,具体涉及一种复合聚酯热熔胶、制备方法及抗冲刷土工布的制备方法。
背景技术
由于土工布具有质量轻、柔性好、强度高、整体性强且不易腐烂的优点,在工程中具有反滤、排水、隔离、增强和防渗等作用,可提高工程质量,因此广泛应用于水利、水运、公路、建筑等工程领域。
其中聚酯类热熔胶常常被用于土工布的粘合加工,其制备方法主要是包括直接酯化缩聚法和酯交换缩聚法,其中酯交换缩聚法合成过程中会生成低分子量有毒物质对环境造成污染,因此在应用上存在一定限制。而现有的通过直接酯化缩聚法得到的聚酯类热熔胶,普遍存在粘接强度低、固化速度慢、抗冲刷性能差的问题。
此外,目前我国水利工程使用的土工布存在抗冲刷强度低、保土性能差防护能力差、使用寿命短的问题,已经无法满足人们对土工布的高要求。
发明内容
本发明的目的是提供一种复合聚酯热熔胶、制备方法及抗冲刷土工布的制备方法,以解决现有聚酯类热熔胶普遍存在粘接强度低、固化速度慢、抗冲刷性能差的问题以及土工布存在抗冲刷强度低、保土性能差、防护能力差、使用寿命短的问题。
本发明解决上述技术问题的技术方案如下:
一种复合聚酯热熔胶的制备方法,其包括以下步骤:
(1)将二元酸和二元醇在钛/钴复合催化剂作用下,在氮气保护下进行酯化反应,反应温度为180℃~200℃,当酯化反应馏出水为理论出水量的95%~98%时,酯化反应结束得到酯化产物;
其中,二元酸和二元醇的质量比为1:(1.2-1.5);
二元酸为对苯二甲酸、间苯二甲酸和2-苯基戊二酸的混合物,其各自加入量的摩尔比为1:(0.10-0.30):(0.10-0.30);
二元醇为二乙烯己二醇、二甘醇和1,4-丁二醇的混合物,其各自加入量的摩尔比为(1.0-1.2):(0.5-0.7):(0.2-0.4);
(2)保温30min~50min后向酯化产物中加入稳定剂,继续升高反应温度至230℃~240℃,在80Pa~100Pa减压进行缩聚反应,反应1.5h~3h后得到聚酯热熔胶;
(3)在常压且氮气保护下,向聚酯热熔胶中加聚甲基丙烯酸甲酯微球在温度在230℃~240℃混合搅拌1h-1.5h,得到复合聚酯热熔胶。
进一步地,在本发明较佳的实施例中,上述步骤(1)中钛/钴复合催化剂由钴系催化剂与钛系催化剂复合,硅系催化剂为醋酸钴,钛系催化剂包括钛酸四丁酯、钛酸四异丙酯或钛酸四甲酯;钛/钴复合催化剂加入量为二元酸总质量的0.01%~0.03%,且钛系催化剂占钛/钴复合催化剂的65-75wt%,其余量为钴系催化剂。
进一步地,在本发明较佳的实施例中,上述步骤(2)中稳定剂为亚磷酸三苯酯或磷酸三甲酯。
进一步地,在本发明较佳的实施例中,上述步骤(3)中聚甲基丙烯酸甲酯微球的加入量是聚酯热熔胶的0.5wt%-1wt%。
进一步地,在本发明较佳的实施例中,上述步骤(3)中聚酯热熔胶还同时加入葡萄糖酸内酯。
进一步地,在本发明较佳的实施例中,上述葡萄糖酸内酯的加入量是聚酯热熔胶的0.1wt%-0.3wt%。
进一步地,在本发明较佳的实施例中,上述聚甲基丙烯酸甲酯微球的粒径为5μm-10μm。
采用上述的复合聚酯热熔胶的制备方法制备得到的复合聚酯热熔胶。
一种抗冲刷土工布的制备方法,采用上述的复合聚酯热熔胶,其包括以下步骤:
将复合聚酯热熔胶与水熔融混合后喷涂到聚对苯二甲酸乙二醇脂编织布上,并静置1min-3min后与聚丙烯土工布在进行在压力为50Kgf-300Kgf下压合1min-5min。
进一步地,在本发明较佳的实施例中,上述复合聚酯热熔胶和水加入量的质量比为3-4:1。
本发明具有以下有益效果:
1、本发明采用具有直链结构的2-苯基戊二酸和二乙烯己二醇对聚酯热熔胶进行改性,能有效提高聚酯热熔胶的粘结强度,同时还可以降低聚酯高分子链的刚性,改善其柔顺性,从而降低其玻璃化转变温度,从而提高其固化速度。
2、本发明采用聚甲基丙烯酸甲酯微球具有强度大、耐冲击性好的优点,在与聚酯热熔胶共混得到复合聚酯热熔胶能显著提高复合聚酯热熔胶的抗冲击性能。此外,聚甲基丙烯酸甲酯微球作为有机改性添加剂,其还能通过与聚酯热熔胶的协同作用,增强复合聚酯热熔胶的粘结强度。
3、本发明采用由钴系催化剂与钛系催化剂复合的钛/钴复合催化剂,钛系催化剂为主催化剂用于加快酯化放应进程,钴系催化剂为助催化剂用于防止聚酯分解产生其他物质降低主催化剂的催化活性。
4、本发明的复合聚酯热熔胶中还添加了葡萄糖酸内酯作为促进剂,促进聚甲基丙烯酸甲酯微球和聚酯热熔胶的共混进程,同时还能提高复合聚酯热熔胶的粘结强度和固化速度。
5、本发明采用聚对苯二甲酸乙二醇脂编织布和聚丙烯土工布均具有耐高温、不吸水性、耐冲击性和无毒性的优点,并通过复合聚酯热熔胶相粘合,得到高抗冲刷强度高、保土性能好、防护能力强、使用寿命长的的抗冲刷土工布。
具体实施方式
以下结合实施例对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1:
本实施例的复合聚酯热熔胶的制备方法,包括以下步骤:
(1)将二元酸和二元醇在钛/钴复合催化剂作用下,在氮气保护下进行酯化反应,反应温度为180℃,当酯化反应馏出水为理论出水量的95%时,酯化反应结束得到酯化产物。
其中,二元酸和二元醇的质量比为1:1.2;
二元酸为对苯二甲酸、间苯二甲酸和2-苯基戊二酸的混合物,其各自加入量的摩尔比为1:0.10:0.10。
二元醇为二乙烯己二醇、二甘醇和1,4-丁二醇的混合物,其各自加入量的摩尔比为1.0:0.5:0.2。
钛/钴复合催化剂由钴系催化剂与钛系催化剂复合,硅系催化剂为醋酸钴,钛系催化剂包括钛酸四丁酯、钛酸四异丙酯或钛酸四甲酯,钛/钴复合催化剂加入量为二元酸总质量的0.01%,且钛系催化剂占钛/钴复合催化剂的65wt%,其余量为钴系催化剂。
(2)保温30min后向酯化产物中加入稳定剂,继续升高反应温度至230℃,减压至80Pa进行缩聚反应,反应1.5h后得到聚酯热熔胶;其中,稳定剂为亚磷酸三苯酯或磷酸三甲酯。
(3)在常压且氮气保护下,向聚酯热熔胶中同时加入聚甲基丙烯酸甲酯微球和葡萄糖酸内酯在温度在230℃混合搅拌1h,得到复合聚酯热熔胶。其中,聚甲基丙烯酸甲酯微球的加入量是复合聚酯热熔胶的0.5wt%,聚甲基丙烯酸甲酯微球的粒径为5μm;葡萄糖酸内酯的加入量是聚酯热熔胶的0.1wt%。
实施例2:
本实施例的复合聚酯热熔胶的制备方法,包括以下步骤:
(1)将二元酸和二元醇在钛/钴复合催化剂作用下,在氮气保护下进行酯化反应,反应温度为190℃,当酯化反应馏出水为理论出水量的97%时,酯化反应结束得到酯化产物。
其中,二元酸和二元醇的质量比为1:1.4;
二元酸为对苯二甲酸、间苯二甲酸和2-苯基戊二酸的混合物,其各自加入量的摩尔比为1:0.20:0.20。
二元醇为二乙烯己二醇、二甘醇和1,4-丁二醇的混合物,其各自加入量的摩尔比为1.1:0.6:0.3。
钛/钴复合催化剂由钴系催化剂与钛系催化剂复合,硅系催化剂为醋酸钴,钛系催化剂包括钛酸四丁酯、钛酸四异丙酯或钛酸四甲酯,钛/钴复合催化剂加入量为二元酸总质量的0.02%,且钛系催化剂占钛/钴复合催化剂的70wt%,其余量为钴系催化剂。
(2)保温40min后向酯化产物中加入稳定剂,继续升高反应温度至235℃,减压至90Pa进行缩聚反应,反应2h后得到聚酯热熔胶;其中,稳定剂为亚磷酸三苯酯或磷酸三甲酯。
(3)在常压且氮气保护下,向聚酯热熔胶中同时加入聚甲基丙烯酸甲酯微球和葡萄糖酸内酯在温度在235℃混合搅拌1h,得到复合聚酯热熔胶。其中,聚甲基丙烯酸甲酯微球的加入量是聚酯热熔胶的0.7wt%,聚甲基丙烯酸甲酯微球的粒径为8μm;葡萄糖酸内酯的加入量是聚酯热熔胶的0.2wt%。
实施例3:
本实施例的复合聚酯热熔胶的制备方法,包括以下步骤:
(1)将二元酸和二元醇在钛/钴复合催化剂作用下,在氮气保护下进行酯化反应,反应温度为200℃,当酯化反应馏出水为理论出水量的98%时,酯化反应结束得到酯化产物。
其中,二元酸和二元醇的质量比为1:1.5;
二元酸为对苯二甲酸、间苯二甲酸和2-苯基戊二酸的混合物,其各自加入量的摩尔比为1:0.30:0.30。
二元醇为二乙烯己二醇、二甘醇和1,4-丁二醇的混合物,其各自加入量的摩尔比为1.2:0.7:0.4。
钛/钴复合催化剂由钴系催化剂与钛系催化剂复合,硅系催化剂为醋酸钴,钛系催化剂包括钛酸四丁酯、钛酸四异丙酯或钛酸四甲酯,钛/钴复合催化剂加入量为二元酸总质量的0.03%,且钛系催化剂占钛/钴复合催化剂的75wt%,其余量为钴系催化剂。
(2)保温50min后向酯化产物中加入稳定剂,继续升高反应温度至240℃,减压至100Pa进行缩聚反应,反应3h后得到聚酯热熔胶;其中,稳定剂为亚磷酸三苯酯或磷酸三甲酯。
(3)在常压且氮气保护下,向聚酯热熔胶中同时加入聚甲基丙烯酸甲酯微球和葡萄糖酸内酯在温度在240℃混合搅拌1.5h,得到复合聚酯热熔胶。其中,聚甲基丙烯酸甲酯微球的加入量是聚酯热熔胶的0.1wt%,聚甲基丙烯酸甲酯微球的粒径为10μm;葡萄糖酸内酯的加入量是聚酯热熔胶的0.3wt%。
实施例4:
本实施例的抗冲刷土工布的制备方法采用实施例1制备的复合聚酯热熔胶,将复合聚酯热熔胶和水以质量比为3:1熔融混合后喷涂到聚对苯二甲酸乙二醇脂编织布上,并静置1min后与聚丙烯土工布在进行在压力为300Kgf下压合1min。
实施例5:
本实施例的抗冲刷土工布的制备方法采用实施例2制备的复合聚酯热熔胶,将复合聚酯热熔胶和水以质量比为3.5:1熔融混合后喷涂到聚对苯二甲酸乙二醇脂编织布上,并静置2min后与聚丙烯土工布在进行在压力为150Kgf下压合3min。
实施例6:
本实施例的抗冲刷土工布的制备方法采用实施例3制备的复合聚酯热熔胶,将复合聚酯热熔胶和水以质量比为4:1熔融混合后喷涂到聚对苯二甲酸乙二醇脂编织布上,并静置3min后与聚丙烯土工布在进行在压力为50Kgf下压合1min。
对照例1:
目前市场上现有的同类型的聚酯热熔胶。
对照例2:
采用对照例1的聚酯热熔胶作为粘合剂以质量比为4:1熔融混合后喷涂到聚丙烯土工布上,并静置3min后与聚丙烯土工布在进行在压力为50Kgf下压合1min,得到复合土工布。
将实施例1-3得到的复合聚酯热熔胶和对照例1得到的聚酯热熔胶分别按照国家标准GB/T4608-84、GB/T3682-2000和部颁标准HG/T3716、FZ/T01085-20000进行检测,其结果如表1所示。
表1实施例1-3和对照例1的检测结果表
Figure GDA0002442890170000071
从表1可以看出,本实施例1-3的复合聚酯热熔胶,其熔点略低于市场上同类型的聚酯热熔胶,但其熔指明显高于对照例1,说明本实施例1-3的复合聚酯热熔胶其粘度更高,且其开放时间和剥离强度也明显优于对照例1的聚酯热熔胶。
将实施例4-6的抗冲刷土工布和对照例2制备的复合土工布以长15cm、宽7.5cm、高9.5cm长方体土工袋形状进行裁剪和缝制,并在土工袋充填等量的黄土,后放入到圆筒冲刷试验仪试坑中每次以不同水流速度进行冲刷30分钟进行抗冲刷测试,其结果如表2所示。
表2实施例4-6和对照例2的抗冲刷试验结果
Figure GDA0002442890170000081
从表2可看出,本实施例4-6制备的抗冲刷土工布其冲刷率和表面积冲刷率低于对照例2的复合土工布,且在经过第六次水流速度为3.3m/s冲刷后,即时长为180分钟的冲刷后,本实施例4-6的抗冲刷土工布缝制的土工袋未出现变形,而对照例2缝制的土工袋已出现变形。
将本实施例5制备的抗冲刷土工布缝制成土工袋进行柔性台阶溢洪道试验,结果表明其最大能抵御流速为5m/s时长600min水流的冲刷,且在在试验结束后柔性台阶溢洪道未发生变形。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,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 (9)

1.一种复合聚酯热熔胶的制备方法,其特征在于,其包括以下步骤:
(1)将二元酸和二元醇在钛/钴复合催化剂作用下,在氮气保护下进行酯化反应,反应温度为180℃~200℃,当酯化反应馏出水为理论出水量的95%~98%时,酯化反应结束得到酯化产物;
其中,二元酸和二元醇的质量比为1:(1.2-1.5);
二元酸为对苯二甲酸、间苯二甲酸和2-苯基戊二酸的混合物,其各自加入量的摩尔比为1:(0.10-0.30):(0.10-0.30);
二元醇为二乙烯己二醇、二甘醇和1,4-丁二醇的混合物,其各自加入量的摩尔比为(1.0-1.2):(0.5-0.7):(0.2-0.4);
(2)保温30min~50min后向酯化产物中加入稳定剂,继续升高反应温度至230℃~240℃,在80Pa~100Pa下减压进行缩聚反应,反应1.5h~3h后得到聚酯热熔胶;
(3)在常压且氮气保护下,向聚酯热熔胶中加入聚甲基丙烯酸甲酯微球在温度为230℃~240℃下混合搅拌1h-1.5h,得到复合聚酯热熔胶;
其中,步骤(3)中聚酯热熔胶还同时加入葡萄糖酸内酯。
2.根据权利要求1所述的复合聚酯热熔胶的制备方法,其特征在于,步骤(1)中钛/钴复合催化剂由钴系催化剂与钛系催化剂复合,钴系催化剂为醋酸钴,钛系催化剂包括钛酸四丁酯、钛酸四异丙酯或钛酸四甲酯;所述钛/钴复合催化剂加入量为二元酸总质量的0.01%~0.03%,且所述钛系催化剂占钛/钴复合催化剂的65wt%-75wt%,其余量为钴系催化剂。
3.根据权利要求1所述的复合聚酯热熔胶的制备方法,其特征在于,步骤(2)中稳定剂为亚磷酸三苯酯或磷酸三甲酯。
4.根据权利要求1所述的复合聚酯热熔胶的制备方法,其特征在于,步骤(3)中聚甲基丙烯酸甲酯微球的加入量是聚酯热熔胶的0.5wt%-1wt%。
5.根据权利要求1所述的复合聚酯热熔胶的制备方法,其特征在于,所述葡萄糖酸内酯的加入量是聚酯热熔胶的0.1wt%-0.3wt%。
6.根据权利要求1-5任一项所述的复合聚酯热熔胶的制备方法,其特征在于,步骤(3)中聚甲基丙烯酸甲酯微球的粒径为5μm-10μm。
7.采用权利要求1-6任一项所述的复合聚酯热熔胶的制备方法制备得到的复合聚酯热熔胶。
8.一种抗冲刷土工布的制备方法,其特征在于,采用如权利要求7所述的复合聚酯热熔胶,其包括以下步骤:
将复合聚酯热熔胶与水熔融混合后喷涂到聚对苯二甲酸乙二醇脂编织布上,并静置1min-3min后与聚丙烯土工布在进行在压力为50Kgf-300Kgf下压合1min-5min。
9.根据权利要求8所述的抗冲刷土工布的制备方法,其特征在于,所述复合聚酯热熔胶和水加入量的质量比为3-4:1。
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