CN115558218B - 一种改性聚氯乙烯、聚氯乙烯静音管及其制备方法 - Google Patents
一种改性聚氯乙烯、聚氯乙烯静音管及其制备方法 Download PDFInfo
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- CN115558218B CN115558218B CN202211124390.4A CN202211124390A CN115558218B CN 115558218 B CN115558218 B CN 115558218B CN 202211124390 A CN202211124390 A CN 202211124390A CN 115558218 B CN115558218 B CN 115558218B
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- polyvinyl chloride
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- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 111
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003607 modifier Substances 0.000 claims abstract description 22
- 239000011256 inorganic filler Substances 0.000 claims abstract description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 14
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 13
- LPXPSTWBTULMJE-UHFFFAOYSA-N n-phenylbutan-1-imine Chemical compound CCCC=NC1=CC=CC=C1 LPXPSTWBTULMJE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000004867 thiadiazoles Chemical class 0.000 claims abstract description 11
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- 239000000843 powder Substances 0.000 claims abstract description 7
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- 239000010920 waste tyre Substances 0.000 claims abstract description 6
- 238000013329 compounding Methods 0.000 claims abstract description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical group [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
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- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 abstract description 7
- 239000000347 magnesium hydroxide Substances 0.000 abstract description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 abstract description 7
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
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- QICVZJNIJUZAGZ-UHFFFAOYSA-N benzene;phosphorous acid Chemical compound OP(O)O.C1=CC=CC=C1 QICVZJNIJUZAGZ-UHFFFAOYSA-N 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
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- 239000004566 building material Substances 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
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- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种改性聚氯乙烯、聚氯乙烯静音管及其制备方法。本发明的改性聚氯乙烯，按重量份数计，由以下组分制备得到：聚氯乙烯100份，增韧剂8～30份，无机填料200～400份，硅藻土2～10份，氢氧化镁1～2份，改性剂0.2～1份，废旧轮胎橡胶粉0～50份，热稳定剂2～5份，润滑剂2～6份，增塑剂15～50份，所述改性剂由噻二唑衍生物和正丁醛苯胺缩合物按质量比(2～3):(0.6～1.2)复配而成。本发明的改性聚氯乙烯采用噻二唑衍生物和正丁醛苯胺缩合物复配作为改性剂，同时与硅藻土相结合，利用硅藻土的吸水特性及其中的MgO以及氢氧化镁与改性剂相互作用形成具有均匀微泡孔的弹性材料，结合材料的高密度可有效阻挡噪声传递，进而提高聚氯乙烯静音管的降噪效果。
Description
技术领域
本发明涉及聚氯乙烯管材的技术领域，更具体地，涉及一种改性聚氯乙烯、聚氯乙烯静音管及其制备方法。
背景技术
聚氯乙烯管材(PVC-U)具有耐酸、耐碱、耐腐蚀性强，耐水压性好，强度高，质轻、流体阻力小，无二次污染，符合卫生要求，施工操作方便，性价比高等优越特性，是全球长期广泛使用的优秀化学建材，主要用于建筑物给排水系统。但PVC-U排水管相较于铸铁排水管排水噪音高于10dB，尤其是在高层住宅排水立管靠近卧室情况下，排水量大，振动源多，水流下落过程形成旋转水膜层及气塞流，使得排水管中空气压力因快速波动而产生噪音；同时水流与排水管壁撞击也会引发振动噪声，严重影响人们居家生活环境质量。
为解决上述排水管噪音问题，一般通过设计排水管的结构或对PVC进行改性。例如现有技术中公开了三层降噪排水管及其制造方法，具体公开了一种由抗冲击外层、降噪音中层和抗冲击内层共挤形成的三层共挤复合管，其中降噪音中层为吸音中层或隔音中层，吸音中层为聚氯乙烯树脂、氯化聚乙烯、铅盐稳定剂、硬质酸钙、硬质酸铅、硬脂酸、石蜡、邻苯二甲酸二辛酯、活性轻质碳酸钙、硫酸钡；隔音中层为聚氯乙烯树脂、甲基丙烯酸酯类聚合物、无机发泡剂，与普通单层PVC排水管相比降噪2.2dB；又如，现有技术还公开了一种硅藻土填充体系PVC降噪排水管，该排水管由三层结构组成，其中外层和内层为沉淀碳酸钙改性PVC材料，芯层为硅藻土改性PVC材料；沉淀碳酸钙填充体系PVC材料由PVC树脂、沉淀碳酸钙、DBP、三碱式亚磷酸钠、亚磷酸苯二异辛酯、三嗪-5、硬脂酸钙、硬脂酸、PE蜡、ACR、金红石型钛白粉制备而成；硅藻土填充体系PVC材料由PVC树脂、硅藻土、DBP、三碱式亚磷酸钠、亚磷酸苯二异辛酯、硬脂酸钙、硬脂酸、PE蜡、ACR、硅烷偶联剂制备而成，但所制成的PVC排水管降噪性能有待进一步提高。
发明内容
本发明的目的是克服现有排水消音管材降噪效果较差的缺陷和不足，提供一种改性聚氯乙烯，采用噻二唑衍生物和正丁醛苯胺缩合物复配作为改性剂，同时与硅藻土相结合，利用硅藻土的吸水特性及其中的MgO以及氢氧化镁与改性剂相互作用形成具有均匀微泡孔的一定交联度的弹性材料，结合材料的高密度可有效阻挡噪声传递，进而提高聚氯乙烯静音管的降噪效果。
本发明的另一目的是提供一种聚氯乙烯静音管。
本发明的又一目的是提供所述聚氯乙烯静音管的制备方法。
本发明上述目的通过以下技术方案实现：
一种改性聚氯乙烯，按重量份数计，由以下组分制备得到：
其中，所述改性剂由噻二唑衍生物和正丁醛苯胺缩合物按质量比(2～3):(0.6～1.2)复配而成。
本发明将噻二唑衍生物与正丁醛苯胺缩合物复配作为改性剂，同时与硅藻土和氢氧化镁等组分相结合改性聚氯乙烯，利用硅藻土的吸水特性及其中的MgO以及氢氧化镁与改性剂共同作用形成微交联弹性的均匀泡孔，结合无机填料后可有效阻挡噪音传递，进而提高聚氯乙烯静音管的降噪效果。
硅藻土中含有少量的Al2O3、Fe2O3、CaO、MgO、K2O、Na2O、P2O5和有机质，且其本身还具有很强的吸水性，在PVC管材熔融挤出过程中，高温(185℃左右)会使得有机物分解及水分挥发而形成泡孔，从而阻挡噪音传递。
本发明改性剂中的噻二唑衍生物为2,5-二巯基-1,3,4-噻二唑衍生物，而正丁醛苯胺缩合物是促进剂，其结构式为C6H5-N＝CH-CH2-CH2-CH3；硅藻土中的MgO+H2O及氢氧化镁可将促进剂正丁醛苯胺缩合物产生的胺盐重新还原成胺，使促进剂起到循环使用的同时，会使得材料发生微交联，并形成比较均匀泡孔，同时可以通过调控改进剂及改性剂中噻二唑衍生物和正丁醛苯胺缩合物的配比控制交联度，与无机填料相结合后可形成密度≥1.8g/cm3，且具有微泡孔的半硬质弹性体改性聚氯乙烯，将其应用于排水管中间层时可有效降低噪音传递。
此外，随着无机填料添加量的增加，虽然有利于提高改性聚氯乙烯的密度，但会影响其他加工性能；而硅藻土的添加量过少时，不利于改性聚氯乙烯中泡孔的形成；硅藻土的添加量过多时，不仅会降低改性聚氯乙烯的密度，还会使其力学性能变差。
优选地，所述改性聚氯乙烯，按重量份数计，由以下组分制备得到：
在具体实施例中，本发明所述聚氯乙烯的聚合度为1000～1100。
在具体实施例中，本发明所述的无机填料的粒径≥800目。
具体地，所述无机填料可以为硫酸钡和/或重质碳酸钙。
具体地，所述增韧剂为氯化聚乙烯，或乙烯-醋酸乙烯酯共聚物(EVA)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、预交联粉末丁腈中至少一种与氯化聚乙烯的混合物。
在熔融共混过程中，改性剂中的正丁醛苯胺缩合物进攻含氯聚合物分子链上的氯原子，同时产生铵盐，含氯聚合物分子则脱氯形成碳碳双键；而改性剂中的噻二唑衍生物则可以打开碳碳双键形成C-S键，而且由于噻二唑衍生物中含有两个巯基，可以形成两个C-S键，从而实现交联形成均匀的泡孔结构，进而有效降低噪音。
具体地，所述热稳定剂为有机锡稳定剂、复合铅盐稳定剂和钙锌复合稳定剂中的一种，具体如熊牌318铅盐稳定剂、鑫达202-1B钙锌稳定剂、青岛东丽T190A有机锡稳定剂；所述润滑剂为硬酯酸、石蜡和PE蜡中的一种或几种。
本发明还保护一种聚氯乙烯静音管，包括内层、中间层和外层，所述中间层由上述改性聚氯乙烯制备得到。
具体地，聚氯乙烯静音管的内层和外层，按重量份数计，由以下组分制备得到：聚氯乙烯100份，抗冲击改性剂0～5份，热稳定剂2～5份，润滑剂0.4～1份，轻质碳酸钙5～20份。其中，抗冲击改性剂具体可以为CPE或核壳改性ACR。此外，还可以根据不同应用场景的实际需求添加颜料组分。
一种聚氯乙烯静音管的制备方法也在本发明的保护范围之内，该制备方法包括以下步骤：
S1.将聚氯乙烯、增韧剂、无机填料、改性剂、废旧轮胎橡胶粉、热稳定剂、润滑剂、增塑剂在90～115℃、600～1000rmp条件下混合以除去易挥发组分，然后加入硅藻土在35～45℃、50～80rmp条件下混合均匀，获得改性聚氯乙烯预混料；加入硅藻土后的混合温度过高，则会导致硅藻土所吸收的水分迅速挥发，不利于后续交联过程中微泡孔的形成；
S2.将聚氯乙烯、抗冲击改性剂、热稳定剂、润滑剂和轻质碳酸钙在90～115℃条件下高速混合以除去易挥发组分，混合均匀即获得聚氯乙烯静音管内层和外层预混料；
S3.将S1中所述改性聚氯乙烯预混料和S2中所述聚氯乙烯静音管内层和外层预混料分别通过锥形双螺杆挤出机塑化后进入三层共挤模具挤出成型，即可获得聚氯乙烯静音管；其中，所述锥形双螺杆挤出机的机筒的温度为165～190℃，主机转速为30～40rmp。
与现有技术相比，本发明的有益效果是：
本发明的改性聚氯乙烯采用噻二唑衍生物和正丁醛苯胺缩合物复配作为改性剂，同时与硅藻土相结合，利用硅藻土的吸水特性及其中的MgO以及氢氧化镁与改性剂相互作用形成具有均匀微泡孔的一定交联度的弹性材料，结合材料的高密度可有效阻挡噪声传递，进而提高聚氯乙烯静音管的降噪效果，将噪音分贝峰值降低至38dB以下。
附图说明
图1为本发明聚氯乙烯静音管的端面结构示意图。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。
聚氯乙烯树脂，聚合度为1000～1100，牌号PVC-SG5，厂家宜宾天原；
氯化聚乙烯，牌号CPE-135A，厂家田东；
乙烯-醋酸乙烯酯共聚物，牌号742，厂家美国杜邦；
硅藻土，牌号SD 8308#，厂家森大；
钙锌稳定剂、邻苯二甲酸二辛酯(DOP)，市售，平行实验中均采用同种；
硫酸钡的粒径为1250目，轻质碳酸钙的粒径为1250目，重质碳酸钙的粒径为1250目，市售，平行实验中均采用同种；
硬脂酸、聚乙烯蜡，市售，平行实验中均采用同种。
实施例1～10
一种改性聚氯乙烯，按重量份数计，由以下组分制备得到，聚氯乙烯、增韧剂、无机填料、改性剂、废旧轮胎橡胶粉、热稳定剂、润滑剂和增塑剂，各组分的具体含量如表1所示。
表1实施例1～10中改性聚氯乙烯的组分(以重量份数计)
一种聚氯乙烯静音管(如图1所示)，包括外层1、中间层2和内层3，中间层2由上述改性聚氯乙烯制备得到，外层1和内层3的按重量份数计，由以下组分制备得到：聚氯乙烯100份，抗冲击改性剂2份，钙锌稳定剂4.5份，硬脂酸0.3份，PE蜡0.3份，轻质碳酸钙20份。
其中，上述聚氯乙烯静音管的直径为110mm，外层厚度为0.7mm，中间层厚度为1.9mm，内层厚度为0.8mm。
上述实施例1～10中的聚氯乙烯静音管可以采用以下制备方法制备：
S1.将聚氯乙烯、增韧剂、无机填料、改性剂、废旧轮胎橡胶粉、热稳定剂、润滑剂、增塑剂在90～115℃条件下高速(600～1000rmp)混合以除去易挥发组分，然后加入硅藻土在35～45℃条件下低速(50～80rmp)混合均匀，获得改性聚氯乙烯预混料；
S2.将聚氯乙烯、热稳定剂、润滑剂和无机填料在90～115℃条件下高速混合以除去易挥发组分，混合均匀即获得聚氯乙烯静音管内层和外层预混料；
S3.将S1中所述改性聚氯乙烯预混料和S2中所述聚氯乙烯静音管内层和外层预混料分别通过锥形双螺杆挤出机塑化后进入三层共挤模具挤出成型，即可获得聚氯乙烯静音管；
其中，所述锥形双螺杆挤出机的机筒的温度为165～190℃，主机转速为30～40rmp。
实施例11
一种改性聚氯乙烯，包括与实施例2相同的组分及含量。
一种聚氯乙烯静音管(如图1所示)，包括外层1、中间层2和内层3，中间层2由上述改性聚氯乙烯制备得到，外层1和内层3的按重量份数计，由以下组分制备得到：聚氯乙烯100份，钙锌稳定剂4.0份，硬脂酸0.2份，PE蜡0.2份，轻质碳酸钙5份。
其中，上述聚氯乙烯静音管的直径为110mm，外层厚度为0.7mm，中间层厚度为1.9mm，内层厚度为0.8mm。
上述聚氯乙烯静音管可以采用以下制备方法制备：
S1.将聚氯乙烯、增韧剂、无机填料、改性剂、废旧轮胎橡胶粉、热稳定剂、润滑剂、增塑剂在90～115℃条件下高速(600～1000rmp)混合以除去易挥发组分，然后加入硅藻土在35～45℃条件下低速(50～80rmp)混合均匀，获得改性聚氯乙烯预混料；
S2.将聚氯乙烯、热稳定剂、润滑剂和轻质碳酸钙在90～115℃条件下高速混合以除去易挥发组分，混合均匀即获得聚氯乙烯静音管内层和外层预混料；
S3.将S1中所述改性聚氯乙烯预混料和S2中所述聚氯乙烯静音管内层和外层预混料分别通过锥形双螺杆挤出机塑化后进入三层共挤模具挤出成型，即可获得聚氯乙烯静音管；
其中，所述锥形双螺杆挤出机的机筒的温度为165～190℃，主机转速为30～40rmp。
对比例1
现有普通国标PVC排水管，型号为Φ110，厂家为雄塑，厚度为3.4mm。
结果检测
制备的聚氯乙烯静音管的噪声检测方法如下：
利用上下2层的试验室进行本发明制得聚氯乙烯静音管的隔音效果测试，平面尺寸为4m×2m，层高为2.4m；下层为测试间，测试件采取多种隔声和吸声措施，然后在测试间内，沿四个墙角分别布置本发明制得的塑料排水管；上层为配管间，布置给水管、排水横支管、三通接头和通气管；供水采用变频调速泵，超声波流量计计量，噪音测试采用NL-22型精密声级计，量程为10～120dB，频率范围为10～20kHz；测试方法采用恒流量长流水的方式，测试流量为1～5L/s，声级计测试探头距地面1.2m，距被测管1m，测试得到排水管发出的噪音分贝峰值。
检测结果如表2所示：
表2检测结果
本发明提供的原料的牌号仅供参考，能够实现本发明技术效果的其他牌号的原料也在本发明的保护范围之内。
本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。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。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。
Claims (10)
1.一种改性聚氯乙烯，其特征在于，按重量份数计，由以下组分制备得到：
其中，所述改性剂由噻二唑衍生物和正丁醛苯胺缩合物按质量比(2～3):(0.6～1.2)复配而成。
2.如权利要求1所述改性聚氯乙烯，其特征在于，按重量份数计，由以下组分制备得到：
3.如权利要求1所述改性聚氯乙烯，其特征在于，所述聚氯乙烯的聚合度为1000～1100。
4.如权利要求1所述改性聚氯乙烯，其特征在于，所述的无机填料的粒径≥800目。
5.如权利要求4所述改性聚氯乙烯，其特征在于，所述无机填料为硫酸钡和/或重质碳酸钙。
6.如权利要求1所述改性聚氯乙烯，其特征在于，所述增韧剂为氯化聚乙烯，或乙烯-醋酸乙烯酯共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物、预交联粉末丁腈中至少一种与氯化聚乙烯的混合物。
7.如权利要求1所述改性聚氯乙烯，其特征在于，所述热稳定剂为有机锡稳定剂、复合铅盐稳定剂和钙锌复合稳定剂中的一种；所述润滑剂为硬酯酸、石蜡和PE蜡中的一种或几种。
8.一种聚氯乙烯静音管，包括内层、中间层和外层，其特征在于，所述中间层由权利要求1～7任一项所述改性聚氯乙烯制备得到。
9.如权利要求8所述聚氯乙烯静音管，其特征在于，所述内层和所述外层按重量份数计，由以下组分制备得到：聚氯乙烯100份，抗冲击改性剂0～5份，热稳定剂2～5份，润滑剂0.4～1.0份，轻质碳酸钙5～20份。
10.一种权利要求9所述聚氯乙烯静音管的制备方法，其特征在于，包括以下步骤：
S1.将聚氯乙烯、增韧剂、无机填料、改性剂、废旧轮胎橡胶粉、热稳定剂、润滑剂、增塑剂在90～115℃条件下混合均匀以除去易挥发组分，然后加入硅藻土在35～45℃条件下混合均匀，获得改性聚氯乙烯预混料；
S2.将聚氯乙烯、抗冲击改性剂、热稳定剂、润滑剂和轻质碳酸钙在90～115℃条件下混合均匀以除去易挥发组分，即获得聚氯乙烯静音管内层和外层预混料；
S3.将S1中所述改性聚氯乙烯预混料和S2中所述聚氯乙烯静音管内层和外层预混料分别通过锥形双螺杆挤出机塑化后进入三层共挤模具挤出成型，即可获得聚氯乙烯静音管；
其中，所述锥形双螺杆挤出机的机筒的温度为165～190℃，主机转速为30～40rmp。
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