WO2024078055A1 - 一种耐磨止滑tpo防水卷材及其制备方法 - Google Patents

一种耐磨止滑tpo防水卷材及其制备方法 Download PDF

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WO2024078055A1
WO2024078055A1 PCT/CN2023/105061 CN2023105061W WO2024078055A1 WO 2024078055 A1 WO2024078055 A1 WO 2024078055A1 CN 2023105061 W CN2023105061 W CN 2023105061W WO 2024078055 A1 WO2024078055 A1 WO 2024078055A1
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wear
slip
resistant
tpo
waterproof membrane
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French (fr)
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朱庆玉
沈梦婷
王仁杰
单永胜
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苏州凯伦高分子新材料科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B10/00—Integration of renewable energy sources in buildings
    • Y02B10/10—Photovoltaic [PV]

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  • the invention relates to a wear-resistant and anti-skid TPO waterproof coiled material and a preparation method thereof.
  • TPO waterproof membrane is very suitable for distributed photovoltaics.
  • TPO waterproof membrane is widely used in waterproof barrier projects. It has good weather resistance, high temperature resistance, low temperature resistance, good flexibility, and good anti-slip performance.
  • the waterproofing membrane surface needs to have good wear resistance, good anti-slip performance, and good weather resistance.
  • the existing TPO membrane is not wear-resistant.
  • the present invention provides a wear-resistant and anti-slip TPO waterproof membrane and a preparation method thereof.
  • the object of the present invention is to provide a wear-resistant and anti-slip TPO waterproof membrane, which is composed of the following components in parts by mass:
  • the density of the TPO elastomer is less than 0.88 g/cm 3 .
  • the SEBS has a star-shaped structure.
  • the elongation at break of the SEBS is not less than 400%.
  • the mass ratio of the total amount of the TPO elastomer and SEBS to PP is 3:7 to 4:6.
  • the light stabilizer is selected from one or more of hindered amines, o-hydroxybenzophenones, and benzotriazoles.
  • the antioxidant is selected from one or more of 2,6-bis(1,1-dimethylethyl)-4-methylphenol, pentaerythritol tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxy)phenylpropionate, and tris(2,4-di-tert-butylphenyl)phosphite.
  • the present invention also provides a method for preparing the wear-resistant and non-slip TPO waterproof membrane, comprising the following steps:
  • step 1) adding the pelletized material obtained in step 1) into the main feed port of the twin-screw extruder, and adding the second mixed material obtained in step 2)
  • the mixed material is added to the side feeding port of the twin-screw extruder, melted and extruded into a sheet through the extruder, and then calendered and cooled by a three-roll system and rolled up to obtain a wear-resistant and non-slip TPO waterproof membrane.
  • the processing temperature of the extruder is 170-200° C.
  • the screw speed is 80 rpm
  • the pulling speed is 12 m/min
  • the particle size of the granulated material is controlled at about 6 mm.
  • the processing temperature of the extruder is 170° C. to 200° C.
  • the screw speed is 15 rpm
  • the pulling speed is 0.9 m/min
  • the tension is controlled at 10N ⁇ 5N.
  • the advantages and beneficial effects of the present invention are: providing a wear-resistant and non-slip TPO waterproof membrane and a preparation method thereof; the TPO waterproof membrane of the present invention has a good static friction coefficient, good non-slip performance, good wear resistance, good weldability, good low-temperature resistance and high-temperature resistance, and is very suitable for photovoltaic roofs for people to walk on.
  • SEBS polypropylene
  • SEBS polypropylene
  • an interpenetrating network structure is formed, which strengthens the physical cross-linking properties.
  • the star-shaped structure is more wear-resistant than the linear structure and exhibits higher abrasion resistance. At the same time, it is softer and has good flexibility, which makes the TPO waterproof membrane have a better static friction coefficient and better anti-slip performance; and it has good low-temperature and high-temperature resistance.
  • SEBS is an amorphous structure with poor surface welding performance. It needs to be blended with TPO elastomer to obtain better welding performance. Therefore, it is necessary to control the content and balance welding efficiency and wear resistance. If too much SEBS is added, the mechanical properties of TPO waterproof membrane (especially elongation at break) will drop rapidly and be lower than the standard of TPO waterproof membrane.
  • TPO elastomer has a wide melting range and low crystallinity. It can improve the flexibility of waterproof membrane and welding efficiency. At the same time, due to its high flexibility and high static friction coefficient, it has good anti-slip performance, which can prevent people on the roof from slipping and falling.
  • the disadvantage of TPO elastomer is that it is not wear-resistant. After a long period of being stepped on by people, the roof will be seriously worn out and there will be hidden dangers of leakage.
  • the star-shaped SEBS is relatively soft and has good dispersibility when blended with TPO materials. Therefore, it still has anti-slip properties and good wear resistance; it is very suitable for photovoltaic roofs where people can walk on it.
  • the traditional method uses wear-resistant additives (such as silicone materials) to achieve the purpose of wear resistance by improving surface lubricity.
  • the traditional method has a loss on welding performance, and the weather resistance and mechanical properties decrease rapidly. It is not suitable for the standards of TPO waterproof membranes and has a counter-effect on anti-slip.
  • the present invention provides a wear-resistant and anti-slip TPO waterproof membrane, which is prepared by the following steps:
  • the density of TPO elastomer is less than 0.88 g/cm 3 ;
  • SEBS has a star-shaped structure, and the elongation at break of SEBS is not less than 400%;
  • the processing temperature of the extruder is 170-200°C, the screw speed is 80rpm, the pulling speed is 12m/min, and the particle size of the granulated material is controlled at about 6mm;
  • the light stabilizer is selected from one or more of hindered amines, o-hydroxybenzophenones, and benzotriazoles;
  • the antioxidant is selected from one or more of 2,6-bis(1,1-dimethylethyl)-4-methylphenol, pentaerythritol tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxy)phenylpropionate, and tris(2,4-di-tert-butylphenyl)phosphite;
  • step 1) adding the granulated material obtained in step 1) to the main feeding port of a twin-screw extruder, and adding the second mixed material obtained in step 2) to the side feeding port of the twin-screw extruder, melting and extruding the sheet through the extruder, and then rolling and cooling the sheet through a three-roll system to obtain a wear-resistant and non-slip TPO waterproof membrane;
  • step 3 Specifically, in step 3):
  • the processing temperature of the extruder is 170°C to 200°C, the screw speed is 15rpm, the traction speed is 0.9m/min, and the tension is controlled at 10N ⁇ 5N.
  • SEBS602 has a star-shaped structure and a hardness of 81ShoreA;
  • SEBS501 has a linear structure and a hardness of 76A.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

本发明公开了一种耐磨止滑TPO防水卷材，按质量份计由以下组分组成：PP20～50份，TPO弹性体20～80份，SEBS5～50份，钛白粉5～20份，光稳定剂0.3～1.5份，抗氧剂0.1～0.8份。本发明还提供上述耐磨止滑TPO防水卷材的制备方法。本发明的TPO防水卷材具有较好的静摩擦系数，止滑性能较好，且耐磨性能好，还具有较好的焊接性，耐低温、耐高温性能都较好，非常适合上人光伏屋面。

Description

一种耐磨止滑TPO防水卷材及其制备方法 技术领域
本发明涉及一种耐磨止滑TPO防水卷材及其制备方法。
背景技术
随着分布式光伏建设的兴起，业主对屋面的使用年限要求越来越高，需要满足屋面与分布式光伏组件同寿命，达到25～30年的使用年限。
TPO防水卷材的防水耐候性非常适合分布式光伏，TPO防水卷材广泛使用于防水阻隔工程，具有耐候性，耐高温，耐低温性能都很好，柔韧性好，具有较好的止滑性能。
然而分布式光伏屋面具有经常上人屋面的需求，需要经常维护，故需要防水卷材表面耐磨性能好，止滑性能好，耐候性能好。而现有TPO卷材不耐磨耗。针对这一点，本发明提供一种耐磨止滑TPO防水卷材及其制备方法。
发明内容
本发明的目的在于提供一种耐磨止滑TPO防水卷材，按质量份计由以下组分组成：
优选的，所述TPO弹性体的密度小于0.88g/cm3。
优选的，所述SEBS为星型结构。
优选的，所述SEBS的断裂伸长率不低于400％。
优选的，所述TPO弹性体和SEBS的总量，与PP的质量比为3:7～4:6。
优选的，所述光稳定剂选自受阻胺类、邻羟基二苯甲酮类、苯并三唑类中的一种或几种。
优选的，所述抗氧剂选自2,6-双(1,1-二甲基乙基)-4-甲基苯酚、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、四(3,5-二叔丁基-4-羟基)苯丙酸季戊四醇酯、三(2,4-二叔丁基苯基)亚磷酸酯中的一种或几种。
本发明还提供上述耐磨止滑TPO防水卷材的制备方法，包括如下步骤：
1)将PP、TPO弹性体、SEBS加入高混机在常温下混合均匀，得到第一混合料；然后将第一混合料加入双螺杆挤出机主喂料口进行共混造粒，得到造粒料；
2)将钛白粉、光稳定剂、抗氧剂加入高混机在常温下混合均匀，得到第二混合料；
3)将步骤1)所得的造粒料加入双螺杆挤出机主喂料口，并将步骤2)所得的第二混 合料加入双螺杆挤出机的侧喂料口，通过挤出机熔融挤出片材，再经三辊系统压延冷却成型后收卷，即得耐磨止滑TPO防水卷材。
优选的，步骤1)中，挤出机的加工温度为170～200℃，螺杆转速为80rpm，牵引速度12m/min，造粒料的粒径控制在6mm左右。
优选的，步骤3)中，挤出机的加工温度为170℃～200℃，螺杆转速为15rpm，牵引速度为0.9m/min，张力控制在10N±5N。
本发明的优点和有益效果在于：提供一种耐磨止滑TPO防水卷材及其制备方法，本发明的TPO防水卷材具有较好的静摩擦系数，止滑性能较好，且耐磨性能好，还具有较好的焊接性，耐低温、耐高温性能都较好，非常适合上人光伏屋面。
SEBS(聚丙乙烯)是一种热塑性嵌段共聚物，因为氢化，耐候性好，具有良好的弹性，因为苯乙烯的加入具有较高的Tg，在和PP、TPO弹性体共混过程中形成互穿网络结构，加强物理交联性能，星型结构比线性结构耐磨，表现出较高的耐磨耗性能，同时较软，具有良好的柔韧性，使TPO防水卷材具有较好的静摩擦系数，止滑性能较好；且耐低温、耐高温性能都较好。
然而SEBS是非晶态结构，表面焊接性能较差，需要和TPO弹性体共混，获得较好的焊接性，因此需要控制含量，平衡焊接效率和耐磨耗性能。若添加过多SEBS，会使TPO防水卷材的机械性能(尤其是断裂伸长率)下降较快，低于TPO防水卷材的标准。
TPO弹性体的熔程很宽，结晶度低，在提高防水卷材柔韧性的同时，能够提升焊接效率，同时因为柔韧性高，静摩擦系数也高，具有很好的止滑性能，能够防止屋面上人作业滑倒摔伤。但TPO弹性体的缺点是并不耐磨耗，屋面经过较长时间的上人踩踏，质量磨损较为严重，会有渗漏的隐患。采用星型SEBS比较软，与TPO材料的共混分散性好，因此仍然具有止滑性能，且耐磨性能好；非常适合上人光伏屋面。
而传统方法采用耐磨助剂(如硅酮材料)，通过提高表面润滑性达到耐磨耗的目的，传统方法对焊接性能有损耗，且耐候性能下降，机械性能下降快，不适合TPO防水卷材的标准，而且对止滑具有反作用。
具体实施方式
下面结合实施例，对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。
本发明提供一种耐磨止滑TPO防水卷材，通过如下步骤制备：
1)将20～50质量份PP、20～80质量份TPO弹性体、5～50质量份SEBS加入高混机在常温下混合均匀，得到第一混合料；然后将第一混合料加入双螺杆挤出机主喂料口进行共混造粒，得到造粒料；
具体的，步骤1)中：
TPO弹性体的密度小于0.88g/cm3；
SEBS为星型结构，且SEBS的断裂伸长率不低于400％；
TPO弹性体和SEBS的总量，与PP的质量比为3:7～4:6；
挤出机的加工温度为170～200℃，螺杆转速为80rpm，牵引速度12m/min，造粒料的粒径控制在6mm左右；
2)将5～20质量份钛白粉、0.3～1.5质量份光稳定剂、0.1～0.8质量份抗氧剂加入高混机在常温下混合均匀，得到第二混合料；
具体的，步骤2)中：
光稳定剂选自受阻胺类、邻羟基二苯甲酮类、苯并三唑类中的一种或几种；
抗氧剂选自2,6-双(1,1-二甲基乙基)-4-甲基苯酚、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、四(3,5-二叔丁基-4-羟基)苯丙酸季戊四醇酯、三(2,4-二叔丁基苯基)亚磷酸酯中的一种或几种；
3)将步骤1)所得的造粒料加入双螺杆挤出机主喂料口，并将步骤2)所得的第二混合料加入双螺杆挤出机的侧喂料口，通过挤出机熔融挤出片材，再经三辊系统压延冷却成型后收卷，即得耐磨止滑TPO防水卷材；
具体的，步骤3)中：
挤出机的加工温度为170℃～200℃，螺杆转速为15rpm，牵引速度为0.9m/min，张力控制在10N±5N。
本发明的具体实施例和对比例如下：
其中：
SEBS602为星型结构，硬度为81ShoreA；
SEBS501为线型结构，硬度为76A。
上述各实施例和对比例的性能如下：
由上表可知，在TPO防水卷材里加入SEBS60215～35份可以实现磨耗和止滑等方面的平衡。
以上所述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，在不脱离本发明技术原理的前提下，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. 一种耐磨止滑TPO防水卷材，其特征在于，按质量份计由以下组分组成：
  2. 根据权利要求1所述的耐磨止滑TPO防水卷材，其特征在于，所述TPO弹性体的密度小于0.88g/cm3。
  3. 根据权利要求1所述的耐磨止滑TPO防水卷材，其特征在于，所述SEBS为星型结构。
  4. 根据权利要求1所述的耐磨止滑TPO防水卷材，其特征在于，所述SEBS的断裂伸长率不低于400％。
  5. 根据权利要求1所述的耐磨止滑TPO防水卷材，其特征在于，所述TPO弹性体和SEBS的总量，与PP的质量比为3:7～4:6。
  6. 根据权利要求1所述的耐磨止滑TPO防水卷材，其特征在于，所述光稳定剂选自受阻胺类、邻羟基二苯甲酮类、苯并三唑类中的一种或几种。
  7. 根据权利要求1所述的耐磨止滑TPO防水卷材，其特征在于，所述抗氧剂选自2,6-双(1,1-二甲基乙基)-4-甲基苯酚、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、四(3,5-二叔丁基-4-羟基)苯丙酸季戊四醇酯、三(2,4-二叔丁基苯基)亚磷酸酯中的一种或几种。
  8. 权利要求1至7中任一项所述耐磨止滑TPO防水卷材的制备方法，其特征在于，包括如下步骤：
    1)将PP、TPO弹性体、SEBS加入高混机在常温下混合均匀，得到第一混合料；然后将第一混合料加入双螺杆挤出机主喂料口进行共混造粒，得到造粒料；
    2)将钛白粉、光稳定剂、抗氧剂加入高混机在常温下混合均匀，得到第二混合料；
    3)将步骤1)所得的造粒料加入双螺杆挤出机主喂料口，并将步骤2)所得的第二混合料加入双螺杆挤出机的侧喂料口，通过挤出机熔融挤出片材，再经三辊系统压延冷却成型后收卷，即得耐磨止滑TPO防水卷材。
  9. 根据权利要求8所述的耐磨止滑TPO防水卷材的制备方法，其特征在于，步骤1)中，挤出机的加工温度为170～200℃，螺杆转速为80rpm，牵引速度12m/min，造粒料的粒径控制在6mm。
  10. 根据权利要求8所述的耐磨止滑TPO防水卷材的制备方法，其特征在于，步骤3)中，挤出机的加工温度为170℃～200℃，螺杆转速为15rpm，牵引速度为0.9m/min，张力控制在10N±5N。
PCT/CN2023/105061 2022-10-10 2023-06-30 一种耐磨止滑tpo防水卷材及其制备方法 WO2024078055A1 (zh)

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