CN102924847B - 一种热可逆交联pvc电缆料及其制备方法 - Google Patents
一种热可逆交联pvc电缆料及其制备方法 Download PDFInfo
- Publication number
- CN102924847B CN102924847B CN201210442938.XA CN201210442938A CN102924847B CN 102924847 B CN102924847 B CN 102924847B CN 201210442938 A CN201210442938 A CN 201210442938A CN 102924847 B CN102924847 B CN 102924847B
- Authority
- CN
- China
- Prior art keywords
- parts
- pvc
- cable material
- stabilizer
- zone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 29
- 230000002441 reversible effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004132 cross linking Methods 0.000 title abstract description 21
- 239000004800 polyvinyl chloride Substances 0.000 title abstract 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000004014 plasticizer Substances 0.000 claims abstract description 11
- 239000011256 inorganic filler Substances 0.000 claims abstract description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000003063 flame retardant Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 13
- 239000010881 fly ash Substances 0.000 claims description 12
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 6
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011324 bead Substances 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 229920000915 polyvinyl chloride Polymers 0.000 abstract 7
- 238000001125 extrusion Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000001514 detection method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical group ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
本发明涉及一种热可逆交联PVC电缆料及其制备方法，所述PVC电缆料由以下组分及重量份数的原料制成：PVC树脂100份；稳定剂2-4份；增塑剂10-40份；无机填料10-50份；热可逆交联剂0.5-5份；润滑剂0.5-2份；抗氧剂0.2-2份；阻燃剂10-30份；该PVC电缆料的制备方法包括配料、高速共混、挤出造粒、干燥等工艺步骤；相对于现有技术，本发明的突出特点是采用一种能发生热可逆交联的PVC专用交联剂与PVC进行共混，然后通过与PVC链上活性氯发生反应引发交联剂、PVC共价交联，从而提高PVC电缆的热稳定性、耐热性并保持原有热塑性。
Description
技术领域
本发明为一种热可逆交联PVC电缆料及其制备方法，属于材料技术领域。
背景技术
随着经济的迅速发展，电线电缆在各个行业、领域中都得到广泛的应用。PVC电缆料价格低廉，性能优良，在电线电缆绝缘保护材料中长期占有重要地位，但是以 PVC为基础的电缆料存在热稳定性差、易老化、耐热性低(Tg～80℃)及软制品的回弹率低等固有缺陷。改善其热稳定性的常用方法是加入铅盐、钙锌稳定剂等，以吸收、稳定分解放出的HCl，而提高其耐热性的常用方法有物理改性(填充、共混)和化学改性(共聚、接枝及交联)。从PVC精细分子结构的观点，PVC的热分解往往是从含活性氯(烯丙基氯或叔碳氯等)的结构处开始，引起自催化脱HCl的连续老化过程，因此设法消除或取代这种(少量)活性氯将可有效地提高PVC材料的热稳定性。PVC的交联是改善其热稳定性并提高力学性能的方法之一。
合理有效的交联可提高PVC材料的使用等级，对PVC电缆料而言，目前研究应用最多的方法是辐照交联法。辐照交联PVC的关键问题是在低辐照剂量下提高凝胶含量，但是PVC材料辐照后存在变色的问题，尤其对于浅色料，辐照后会变色，影响外观，往往不被客户所接受，产生纠纷，增加不必要的生产成本。从另一个方面来讲，传统的交联虽可有效地提高PVC的强度和耐热性，但其最严重的后果是使PVC材料发生永久交联，从而丧失了宝贵的热塑性，由此使PVC变为不可再次回收利用的热固性塑料。
发明内容
本发明的目的主要是解决现有技术所存在的PVC电缆热稳定性差、耐热性不好及形成热固性塑料等问题，提供了一种热可逆交联PVC电缆料及其制备方法。
为实现上述目的，本发明采用如下技术方案：
一种热可逆交联PVC电缆料，由以下组分及重量份数的原料制成：PVC树脂100份；稳定剂2-4份；增塑剂10-40份；无机填料10-50份；热可逆交联剂0.5-5份；润滑剂0.5-2份；抗氧剂0.2-2份；阻燃剂10-30份。
优选地，其中所述PVC树脂为PVC SG-3，所述稳定剂为钙锌稳定剂、稀土稳定剂或有机锡稳定剂中的至少一种。
优选地，所述增塑剂为二辛脂类增塑剂、环氧类增塑剂中的至少一种。
优选地，所述无机填料为粉煤灰或玻璃微珠中的至少一种，其中所述粉煤灰的粒径为5.8μm，比表面积2.230m2/cm3，所述玻璃微珠的粒径为300目。
优选地，所述润滑剂为PE蜡、石蜡、金属皂类或硬脂酸类中的至少一种。
优选地，所述热可逆交联剂为双环戊二烯二羧酸盐DCPD(COOM)2，其中M为K、Na或Li。
优选地，所述抗氧剂为抗氧剂1010。
优选地，所述阻燃剂为氢氧化镁和氢氧化铝中的至少一种。
本发明还提供上述热可逆交联PVC电缆料的制备方法，包括以下步骤：
1)常温下将PVC树脂、稳定剂、增塑剂按比例投入高速混合机混合4-6分钟，升温到90-100℃，然后将无机填料、交联剂、润滑剂、抗氧剂、阻燃剂按比例投入高速混合机中混合3-5分钟，搅拌至100-110℃，立即将混合料进入冷却混合机，混合3-5分钟，出料温度30-40℃；
2)将步骤1)所得混合料送入双螺杆挤出机中进行混炼；
3)最后经双螺杆挤出机挤出、冷却水冷却、切粒机切粒、鼓风干燥得到所述热可逆交联PVC电缆料。
优选地，其中所述双螺杆挤出机的参数设定如下：一区 140-150℃、二区 150-160℃、三区 160-170℃、四区 170-180℃；机头温度 160-170℃；螺杆转速 10-40r/min。
本发明相对于现有技术，其突出特点是采用一种能发生热可逆交联剂与PVC树脂、无机填料等进行共混，通过与活性氯反应引发PVC共价交联，凝胶含量增大，从而提高PVC的热稳定性、耐热性并保持其热塑性；此外，这种交联剂在常温下处于交联状态，而在加工温度下可以解交联，具有热可逆特性，因此，具有良好的可加工性。而且该制备方法更为简便有效，应用更为安全可靠。
具体实施方式
为详细说明本发明的各种有效组分组成、制备方法，列举如下实施例详细说明。
下面结合实施例对本发明作进一步详细说明。
实施例1
常温下将PVC(SG3)(内蒙古亿利化学工业有限公司)100份、钙锌稳定剂(河北精信化工集团有限公司)3份、DOP (邻苯二甲酸二辛酯) (濮阳市诚意增塑剂有限公司)30份投入高速混合机混合4-6分钟升温到90℃左右，然后将粉煤灰(亿利资源集团有限公司自有电厂排放的粉煤灰，粒径约5.8μm，比表面积2.230m2/cm3)20份、热可逆交联剂(成分为双环戊二烯二羧酸盐DCPD(COOM)2，M为K、Na、Li，制备方法请参考Eli Ruckenstein, Xiaonong Chen. Crosslinking of Chlorine-Containing Polymers by Dicyclopentadiene Dicarboxylic Salts[J]. Journal of Polymer Science: Part A: Polymer Chemistry, 2000 (38): 818-825.）1份、PE蜡(PE-Wax，D1100A) (上海纳多化工有限公司)0.5份、抗氧剂1010(北京极易化工有限公司)1.0份、氢氧化镁(大连亚泰科技新材料有限公司)10份投入高速混合机中混合3-5分钟，搅拌至100-110℃，立即放料进入冷却混合机，混合3-5分钟，出料温度30-40℃。将所得混合料送入双螺杆挤出机中进行混炼，双螺杆挤出机各段的加工温度设定如下，一区 145℃、二区 155℃、三区 170℃、四区 180℃、机头温度 170℃、螺杆转速 20 r/min，最后经双螺杆挤出机挤出、冷却水冷却、切粒机造粒、鼓风干燥即得到所需的热可逆交联PVC电缆料。按照国家标准检测，各项指标如表2所示。
实施例2
常温下将PVC(SG3)( 内蒙古亿利化学工业有限公司)100份、钙锌稳定剂(河北精信化工集团有限公司)3份、DOP (邻苯二甲酸二辛酯) (濮阳市诚意增塑剂有限公司)30份投入高速混合机混合4-6分钟升温到90℃左右，然后将粉煤灰(亿利资源集团有限公司自有电厂排放的粉煤灰，粒径约5.8μm，比表面积2.230m2/cm3)20份、热可逆交联剂(成分为双环戊二烯二羧酸盐DCPD(COOM)2，M为K、Na、Li，制备方法请参考Eli Ruckenstein, Xiaonong Chen. Crosslinking of Chlorine-Containing Polymers by Dicyclopentadiene Dicarboxylic Salts[J]. Journal of Polymer Science: Part A: Polymer Chemistry, 2000 (38): 818-825.）2份、PE蜡(PE-Wax，D1100A) (上海纳多化工有限公司)0.5份、抗氧剂1010(北京极易化工有限公司)1.0份、氢氧化镁(大连亚泰科技新材料有限公司)10份投入高速混合机中混合3-5分钟，搅拌至100-110℃，立即放料进入冷却混合机，混合3-5分钟，出料温度30-40℃。将所得混合料送入双螺杆挤出机中进行混炼，双螺杆挤出机各段的加工温度设定如下，一区 145℃、二区 155℃、三区 170℃、四区 180℃、机头温度 170℃、螺杆转速 20 r/min，最后经双螺杆挤出机挤出、冷却水冷却、切粒机造粒、鼓风干燥 即得到所需的热可逆交联PVC电缆料。按照国家标准检测，各项指标如表2所示。
实施例3
常温下将PVC(SG3)( 内蒙古亿利化学工业有限公司)100份、钙锌稳定剂(河北精信化工集团有限公司)3份、环氧大豆油 (河北翰兴化工有限公司)40份投入高速混合机混合4-6分钟升温到90℃左右，然后将粉煤灰(亿利资源集团有限公司自有电厂排放的粉煤灰，粒径约5.8μm，比表面积2.230m2/cm3)20份、热可逆交联剂(成分为双环戊二烯二羧酸盐DCPD(COOM)2，M为K、Na、Li，制备方法请参考Eli Ruckenstein, Xiaonong Chen. Crosslinking of Chlorine-Containing Polymers by Dicyclopentadiene Dicarboxylic Salts[J]. Journal of Polymer Science: Part A: Polymer Chemistry, 2000 (38): 818-825.）2份、PE蜡(PE-Wax，D1100A) (上海纳多化工有限公司)0.5份、抗氧剂1010(北京极易化工有限公司)1.0份、氢氧化镁(大连亚泰科技新材料有限公司)10份投入高速混合机中混合3-5分钟，搅拌至100-110℃，立即放料进入冷却混合机，混合3-5分钟，出料温度30-40℃。将所得混合料送入双螺杆挤出机中进行混炼，双螺杆挤出机各段的加工温度设定如下，一区 145℃、二区 155℃、三区 170℃、四区 180℃、机头温度 170℃、螺杆转速 20 r/min，最后经双螺杆挤出机挤出、冷却水冷却、切粒机造粒、鼓风干燥即得到所需的热可逆交联PVC电缆料。按照国家标准检测，各项指标如表2所示。
实施例4
常温下将PVC(SG3)( 内蒙古亿利化学工业有限公司)100份、钙锌稳定剂(河北精信化工集团有限公司)3份、环氧大豆油 (河北翰兴化工有限公司)30份投入高速混合机混合4-6分钟升温到90℃左右，然后将粉煤灰(亿利资源集团有限公司自有电厂排放的粉煤灰，粒径约5.8μm，比表面积2.230m2/cm3)30份、热可逆交联剂(成分为双环戊二烯二羧酸盐DCPD(COOM)2，M为K、Na、Li，制备方法请参考Eli Ruckenstein, Xiaonong Chen. Crosslinking of Chlorine-Containing Polymers by Dicyclopentadiene Dicarboxylic Salts[J]. Journal of Polymer Science: Part A: Polymer Chemistry, 2000 (38): 818-825.）1份、PE蜡(PE-Wax，D1100A) (上海纳多化工有限公司)0.5份、抗氧剂1010(北京极易化工有限公司)1.0份、氢氧化铝(大连亚泰科技新材料有限公司)20份投入高速混合机中混合3-5分钟，搅拌至100-110℃，立即放料进入冷却混合机，混合3-5分钟，出料温度30-40℃。将所得混合料送入双螺杆挤出机中进行混炼，双螺杆挤出机各段的加工温度设定如下，一区 145℃、二区 155℃、三区 170℃、四区 180℃、机头温度 170℃、螺杆转速 10 r/min，最后经双螺杆挤出机挤出、冷却水冷却、切粒机造粒、鼓风干燥即得到所需的热可逆交联PVC电缆料。按照国家标准检测，各项指标如表1所示。
表1热可逆交联PVC电缆料性能检测结果
| 性能指标 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
| 凝胶含量(%) | 41 | 67 | 60 | 75 |
| 拉伸强度(MPa) | 19.27 | 20.21 | 19.75 | 22.08 |
| 冲击强度(KJ/m2) | 4.06 | 8.17 | 7.65 | 10.33 |
| 断裂伸长率(%) | 192 | 168 | 175 | 143 |
| 维卡软化温度(℃) | 70.12 | 73.56 | 65.39 | 76.47 |
由表1可以看出，随着交联剂用量的增加，PVC制品的凝胶含量、拉伸强度、冲击强度和维卡软化温度随之提高，断裂伸长率减小，说明交联剂的添加使PVC分子发生交联，力学性能和热性能得到增强。当增塑剂用量增多时，PVC制品较软，力学性能较低。当加工时间，即混合料在双螺杆挤出机中停留时间延长时，有利于交联剂引发PVC分子链进行交联，从而使力学性能和热性能得到增强。
以上所述，仅为本发明的实施例，应当指出，对于本技术中的普通技术人员来说，在不脱离本发明的核心技术特征的前提下，还可以做若干的改进和润饰，这些润饰和改进也应属于本发明的专利保护范围。
Claims (1)
1.一种热可逆交联PVC电缆料，其特征在于，所述热可逆交联PVC电缆料由以下组分及重量份数的原料制成：PVC树脂100份；稳定剂2-4份；增塑剂10-40份；无机填料10-50份；热可逆交联剂0.5-5份；润滑剂0.5-2份；抗氧剂0.2-2份；阻燃剂10-30份；其中，
所述PVC树脂为PVC SG-3；所述稳定剂为钙锌稳定剂、稀土稳定剂或有机锡稳定剂中的至少一种；所述增塑剂为二辛脂类增塑剂、环氧类增塑剂的至少一种；所述无机填料为粉煤灰和玻璃微珠中的至少一种，其中所述粉煤灰的粒径为5.8μm，比表面积为2.230m2/cm3；所述玻璃微珠的粒径为300目；所述热可逆交联剂为双环戊二烯二羧酸盐DCPD(COOM)2，其中M为K、Na或Li；所述润滑剂为PE蜡、石蜡、金属皂类或硬脂酸类中的至少一种；所述抗氧剂为抗氧剂1010；所述阻燃剂为氢氧化镁或氢氧化铝中的至少一种；
通过以下步骤制得：
1)常温下将PVC树脂、稳定剂、增塑剂按比例投入高速混合机混合4-6分钟升温到90-100℃，然后将无机填料、交联剂、润滑剂、抗氧剂、阻燃剂按比例投入高速混合机中混合3-5分钟，搅拌至100-110℃，立即将混合料进入冷却混合机，混合3-5分钟，出料温度30-40℃；
2)将步骤1)所得混合料送入双螺杆挤出机中进行混炼；
3)最后经双螺杆挤出机挤出、冷却水冷却、切粒机切粒、鼓风干燥得到所述热可逆交联PVC电缆料；其中所述双螺杆挤出机的参数设定如下：一区 140-150℃、二区 150-160℃、三区 160-170℃、四区 170-180℃；机头温度 160-170℃；螺杆转速 10-40r/min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210442938.XA CN102924847B (zh) | 2012-11-08 | 2012-11-08 | 一种热可逆交联pvc电缆料及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210442938.XA CN102924847B (zh) | 2012-11-08 | 2012-11-08 | 一种热可逆交联pvc电缆料及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102924847A CN102924847A (zh) | 2013-02-13 |
| CN102924847B true CN102924847B (zh) | 2015-06-03 |
Family
ID=47639787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210442938.XA Active CN102924847B (zh) | 2012-11-08 | 2012-11-08 | 一种热可逆交联pvc电缆料及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102924847B (zh) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448603A (zh) * | 2013-12-19 | 2015-03-25 | 惠州乐庭电子线缆有限公司 | 一种透明阻燃交联聚氯乙烯电线电缆料及其制备方法 |
| CN104004304B (zh) * | 2014-06-23 | 2017-01-25 | 北京化工大学 | 一种具有形状记忆功能的pvc材料 |
| CN104231501A (zh) * | 2014-09-30 | 2014-12-24 | 句容金猴机械研究所有限公司 | 一种合成树脂瓦及其制备方法 |
| CN104974448A (zh) * | 2015-07-08 | 2015-10-14 | 常州市诚天电子有限公司 | 一种基于pvc材质的电缆材料及其之制备方法 |
| CN105462111A (zh) * | 2015-12-15 | 2016-04-06 | 中冠电缆有限公司 | 一种含改性粉煤灰的pvc电缆料及其制备方法 |
| CN106349592A (zh) * | 2016-08-24 | 2017-01-25 | 付竹兰 | 一种聚氯乙烯电缆料的制造方法 |
| CN106349595A (zh) * | 2016-08-24 | 2017-01-25 | 付竹兰 | 一种阻燃聚氯乙烯电缆料及其制备方法 |
| CN107189097B (zh) * | 2017-06-19 | 2019-04-26 | 北京化工大学 | 一种具有热可逆交联结构的复合热稳定剂及其制备与应用 |
| CN110041644B (zh) * | 2019-05-08 | 2021-07-02 | 上海擎木新材料科技有限公司 | 一种多尺度复合填充热可逆交联pvc材料及制备方法 |
| WO2021159438A1 (en) * | 2020-02-14 | 2021-08-19 | Sika Technology Ag | Thermoreversibly crosslinked polyvinylchloride membrane |
| CN111253698B (zh) * | 2020-04-07 | 2022-06-03 | 安徽弘宜新材料科技发展有限公司 | Pvc多功能交联电缆护套料及其加工工艺 |
| CN112080085A (zh) * | 2020-08-28 | 2020-12-15 | 宝胜科技创新股份有限公司 | 一种5g电缆用高阻燃聚氯乙烯绝缘料及其制备方法 |
| CN113429721A (zh) * | 2021-07-16 | 2021-09-24 | 江苏宝安电缆有限公司 | 一种接枝反应挤出生产高耐磨性pvc制品及其方法 |
| CN113912964A (zh) * | 2021-11-23 | 2022-01-11 | 苏州爱得华塑化有限公司 | Ev液冷可逆变交联弹性体缆料 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811960A (zh) * | 2010-04-20 | 2010-08-25 | 北京化工大学 | 一种羧酸盐热可逆交联剂及其制备方法 |
| CN101857705A (zh) * | 2010-06-23 | 2010-10-13 | 深圳市帝源电子有限公司 | 无毒、抗热收缩聚氯乙烯材料及其制造工艺 |
| CN101885881A (zh) * | 2010-05-05 | 2010-11-17 | 深圳市联嘉祥科技股份有限公司 | 一种耐热阻燃聚氯乙烯电缆料及其制作方法 |
-
2012
- 2012-11-08 CN CN201210442938.XA patent/CN102924847B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811960A (zh) * | 2010-04-20 | 2010-08-25 | 北京化工大学 | 一种羧酸盐热可逆交联剂及其制备方法 |
| CN101885881A (zh) * | 2010-05-05 | 2010-11-17 | 深圳市联嘉祥科技股份有限公司 | 一种耐热阻燃聚氯乙烯电缆料及其制作方法 |
| CN101857705A (zh) * | 2010-06-23 | 2010-10-13 | 深圳市帝源电子有限公司 | 无毒、抗热收缩聚氯乙烯材料及其制造工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102924847A (zh) | 2013-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102924847B (zh) | 一种热可逆交联pvc电缆料及其制备方法 | |
| CN101645319B (zh) | 一种电线电缆用环保型耐热复合弹性电缆料及其制备方法 | |
| CN103333406B (zh) | 一种改性膨胀阻燃聚丙烯组合物及其制备方法 | |
| CN104312038B (zh) | 超耐热耐油型聚氯乙烯电缆料及其制备方法、电缆 | |
| CN102532763A (zh) | 氯化聚氯乙烯改性材料，其制备方法及用途 | |
| CN103059404A (zh) | 辐照交联低烟无卤阻燃聚烯烃绝缘料及其制备方法 | |
| CN111171542B (zh) | 一种高cti阻燃聚碳酸酯合金材料及其制备方法和用途 | |
| CN106009585A (zh) | 一种无卤阻燃的聚碳酸酯材料及其制备方法 | |
| CN112143122A (zh) | 耐热环保阻燃电缆绝缘料及其制备方法 | |
| CN114672131B (zh) | 一种自动微交联无卤阻燃热塑性弹性体及其制备方法 | |
| CN105034186B (zh) | 光伏线缆护套层材料的制备方法 | |
| CN104356538B (zh) | 一种阻燃消烟的聚氯乙烯电线电缆料 | |
| CN104387672A (zh) | 一种再生聚丙烯阻燃改性材料及其制备方法 | |
| CN104262851A (zh) | 汽车原线用耐磨辐照交联聚氯乙烯绝缘料及其制备方法 | |
| CN113956588B (zh) | 抗老化阻燃pvc材料及用于电线或电缆制备方法、用途 | |
| CN1908062A (zh) | 一种无卤低烟阻燃abs功能母粒及加工工艺 | |
| CN1908060A (zh) | 阻燃丙烯腈－苯乙烯共聚树脂/丙烯腈－氯化聚乙烯－苯乙烯共聚树脂塑料合金的制造方法 | |
| CN102977479A (zh) | 动态交联阻燃性氯化聚乙烯热塑性弹性体的制备方法 | |
| CN112143124A (zh) | 一种聚氯乙烯复合电缆绝缘材料及其制备方法和应用 | |
| CN112143032B (zh) | 一种改性氢氧化铝、阻燃聚氯乙烯材料及其制备方法 | |
| CN113956564A (zh) | 易加工抗滴落低烟无卤阻燃聚烯烃隔氧料及其制备方法 | |
| CN104086916B (zh) | 用于电力系统的环保型的聚氯乙烯电缆材料及其生产方法 | |
| CN105885430A (zh) | 一种高耐磨抗拉环保型高铁电缆材料 | |
| CN105462225A (zh) | 防静电pc/pbt合金材料及其制备方法和安全鞋头 | |
| CN105778239A (zh) | 一种陶瓷化聚烯烃阻燃耐火电缆材料 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220330 Address after: 017209 mingziliang village, Ulan Mulun Town, Yiqi, Ordos City, Inner Mongolia Autonomous Region Patentee after: Ordos Zhibo Machinery Manufacturing Co.,Ltd. Address before: 100031 6th Floor, Kaichen World Trade Center East Block, 28 Fuxing Mennei Street, Xicheng District, Beijing Patentee before: ELION RESOURCES Group |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220412 Address after: 014300 Dalate circular economy industrial park of Yili Group, Shulinzhao Town, Dalate Banner, Ordos City, Inner Mongolia Autonomous Region Patentee after: INNER MONGOLIA ELION CHEMICAL INDUSTRY CO.,LTD. Address before: 100031 6th Floor, Kaichen World Trade Center East Block, 28 Fuxing Mennei Street, Xicheng District, Beijing Patentee before: ELION RESOURCES Group |