CN112280211A - 一种成碳性良好的pvc电缆料及其制备方法 - Google Patents
一种成碳性良好的pvc电缆料及其制备方法 Download PDFInfo
- Publication number
- CN112280211A CN112280211A CN202011131391.2A CN202011131391A CN112280211A CN 112280211 A CN112280211 A CN 112280211A CN 202011131391 A CN202011131391 A CN 202011131391A CN 112280211 A CN112280211 A CN 112280211A
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- Prior art keywords
- parts
- flame retardant
- polyvinyl chloride
- carbon
- cable material
- Prior art date
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 97
- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 71
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 70
- 239000003063 flame retardant Substances 0.000 claims abstract description 64
- 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 abstract description 61
- 239000004014 plasticizer Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000012745 toughening agent Substances 0.000 claims abstract description 6
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 5
- -1 tetrabromobenzene anhydride ester Chemical group 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 11
- 229910019142 PO4 Chemical group 0.000 claims description 7
- 239000010452 phosphate Chemical group 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000004801 Chlorinated PVC Substances 0.000 claims description 4
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 4
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 125000005591 trimellitate group Chemical group 0.000 claims description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 4
- 239000008158 vegetable oil Substances 0.000 claims description 4
- BHSXLOMVDSFFHO-UHFFFAOYSA-N (3-ethylsulfanylphenyl)methanamine Chemical compound CCSC1=CC=CC(CN)=C1 BHSXLOMVDSFFHO-UHFFFAOYSA-N 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229940071182 stannate Drugs 0.000 claims description 3
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 claims description 2
- 229920003314 Elvaloy® Polymers 0.000 claims description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims description 2
- 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 compound 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 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 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
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 150000008301 phosphite esters Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
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- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 7
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- 239000007789 gas Substances 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
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- 229910052739 hydrogen Inorganic materials 0.000 description 4
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
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- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
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- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical group CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- 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
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Abstract
一种成碳性良好的PVC电缆料，其特征在于：主要由以下重量份数的物质组成：100份聚氯乙烯树脂，20‑40份增塑剂a，10‑30份增塑剂b，5‑15份阻燃剂a，5‑15份阻燃剂b，5‑15份成碳剂a，5‑15份，成碳剂b，0.1‑2份抗氧剂，还可以包括10‑40份填料a，10‑40份填料b，2‑10份热稳定剂，0.3‑2份润滑剂，5‑10份增韧剂。其成碳性高，碳层致密、厚实，使PVC的阻燃从阻燃材料迈向防火材料高端市场，能解决目前各类大量含有易燃物质的网络线、高压电力电缆等产品高阻燃要求。
Description
技术领域
本发明属于电缆材料技术领域，特别涉及一种成碳性良好的PVC电缆料及其制备方法。
背景技术
聚氯乙烯(PVC)是一种含卤高分子材料。目前市面上可以买到的纯PVC是颗粒状材料，其机械强度高，拥有非常好的防气候变化、防水、防化学品性能，是一种良好的电绝缘材料。虽然聚氯乙烯材料对光和热敏感，但通过加入安定剂(稳定剂)即可提高其光热稳定性。如果从分子结构考虑，一方面，PVC中含有卤素，所以其显示出优异的阻燃性能，另一方面，聚氯乙烯脱去氯化氢或氢自由基后会形成路易斯酸结构，使其具有较低的成碳温度。
PVC电缆料主要由PVC树脂和增塑剂组成。在进行PVC电缆料燃烧实验时，增塑剂遵循气相阻燃机理直接被燃烧，PVC树脂则是先熔融再燃烧成碳。而由于熔融的PVC树脂具有滴流的特性，增塑剂的燃烧会导致较为明显的成碳体积收缩以及碳层坍塌破裂。这也是软质PVC的成碳效果远不如硬质PVC的原因之一。
众所周知，高聚物成碳对阻燃起着重要的作用。一般而言，成碳率高的聚合物，其氧指数较高。碳的生成本身就对热降解起着重要的作用。碳生成后，会在高聚物的表面形成粘附的绝缘碳层，此碳层可以使得高聚物和火焰隔绝。换言之，成碳性好的电缆料可以更加进行更加高效的阻燃。
PVC成碳的形成是一个相当复杂的过程，且PVC成碳的研究在国内进行的相对较少，没有什么理论可以进行支持。目前，国内外更多研究的是低烟无卤材料的成碳性能且聚烯烃类成碳也是不成熟的理论，很多现象无法解释。
随着阻燃技术的发展，人们从追求简单的氧指数阻燃转变成追求模拟环境阻燃，从简单的难燃发展为火灾时电缆依然能正常工作。而市场上常规的PVC电缆料已经无法满足目前高端市场需求。V0(防火等级)、VW-1(耐燃等级)、CMR(防火等级)、CMP(防火等级)等标准的实行都在进一步推动PVC成碳研究的需要。
常规磷氮阻燃剂对于低烟无卤材料、聚碳酸酯、工程塑料有良好的成碳结核效果。但是常规磷氮阻燃剂在PVC内部使用时存在几个问题：1.磷氮阻燃剂延缓了PVC成碳速率，但却增加了PVC在高温下的滴流程度，外层塑料将因为滴流被重力拉伸变薄；2.增塑剂在燃烧时仍遵循气相阻燃机理，气化燃烧导致碳层进一步变薄；3.氮元素形成微孔使碳层膨胀，熔体比较薄时形成的气孔导致碳层出现裂纹甚至完全破裂脱落。
有鉴于此，如何设计一种成碳性良好的PVC电缆料是本发明研究的课题。
发明内容
本发明提供了一种成碳性良好的PVC电缆料及其制备方法，其目的是要解决现有电缆料阻燃性能达不到高端市场需求的问题。
为达到上述目的，本发明采用的技术方案是：1.一种成碳性良好的PVC电缆料，其特征在于：主要由以下重量份数的物质组成：
所述增塑剂a为偏苯三酸酯、对苯二甲酸二辛酯、邻苯二甲酸二异壬酯、植物油酯中的一种或几种；
所述增塑剂b为四溴苯酐酯和/或磷酸酯类增塑剂；
所述阻燃剂a为三氧化二锑、硅酸盐类阻燃剂、三氧化钼中的一种或几种；所述阻燃剂b为硼酸锌、碱式碳酸镁、锡酸硅、锡酸镁、蒙脱土中的一种或几种；
所述成碳剂a为苯氧基聚磷腈和/或六苯氧环三磷腈；成碳剂b为聚苯醚。
以下是对本技术方案的解释说明：
1.上述方案中，所述聚氯乙烯树脂包括聚氯乙烯均聚物和/或聚氯乙烯共聚物；所述聚氯乙烯均聚物为悬浮聚合聚氯乙烯、乳液聚合聚氯乙烯、氯化聚氯乙烯；聚氯乙烯共聚物包括氯醋树脂、氯化聚乙烯。
2.上述方案中，所述磷酸酯类增塑剂为磷酸三苯酯、磷酸三甲苯酯、磷酸三(2,3-二溴丙基)酯。
3.上述方案中，还包括2-10份热稳定剂，所述热稳定剂为亚磷酸酯类稳定剂和/或钙锌稳定剂。
4.上述方案中，还包括0.1-2份抗氧剂，所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂1024、抗氧剂1098中的一种或几种。
5.上述方案中，还包括5-10份增韧剂，所述增韧剂为美国杜邦牌号Elvaloy HP441增韧剂、α-甲基苯乙烯-丙烯腈共聚物、氯化聚乙烯中的一种或几种。。
6.上述方案中，还包括0.3-2份润滑剂，所述润滑剂为硬脂酸、季戊四醇硬脂酸酯、聚乙烯蜡、硬脂酸钙、氧化聚乙烯中的一种或几种。
7.上述方案中，所述植物油脂为柠檬酸三酯、环氧脂肪酸甲酯。
8.上述方案中，可以添加加工改性剂1-5份，所述加工改性剂为ACR401和/或ATL-95。
9.上述方案中，成碳剂b为磷氮含量30％-40％的聚苯醚。
10.上述方案中，所述硅酸盐类阻燃剂为硅酸锡、硅酸镁。
11.上述方案中，还包括10-40份填料a，所述填料a为碳酸钙；10-40份填料b，所述填料b为氢氧化铝、氢氧化镁、滑石粉的一种或几种。
12.上述方案中，亚磷酸酯类稳定剂和钙锌稳定剂是指不含铅等重金属元素的环保型稳定剂。
13.一种成碳性良好的PVC电缆料的制备方法，其特征在于，包括以下步骤：
按配方比例计量称重得到原辅材料；将计量称重好的原辅材料放入高速捏合机中高速摩擦下升温至130至140℃进行高速捏合，充分混合均匀和预塑化；放入双螺杆挤出机组130—160℃下进行挤出混炼塑化；100—130℃下单螺杆造粒。
本发明的设计原理和效果：
1.本发明技术方案中所述聚氯乙烯树脂包括聚氯乙烯均聚物和/或聚氯乙烯共聚物；包含聚氯乙烯单体的聚氯乙烯共聚物理论上均适用于本发明技术方案，其中氯含量越高阻燃成碳性越优异、机械性能越高、耐磨耐刮性能越好。
2.本发明技术方案使用了两类增塑剂，增塑剂a(偏苯三酸酯、对苯二甲酸二辛酯、邻苯二甲酸二异壬酯、植物油酯)为常规增塑剂，用于降低PVC玻璃转化点，使PVC更柔顺和加工性能更优秀；增塑剂b(四溴苯酐酯和/或磷酸酯类增塑剂)为阻燃增塑剂，属于溴系阻燃剂/磷酸系列的阻燃剂，此类阻燃剂能够在赋予PVC柔顺性的同时赋予阻燃性，磷系阻燃剂能够在燃烧过程中形成的焦磷酸盐有助于形成碳层，溴系阻燃剂的特点在于溴的气相阻燃作用大于氯的作用，能大幅提高产品的气相阻燃效率。
3.本发明技术方案使用了两类阻燃剂，阻燃剂a(三氧化二锑、硅酸盐类、三氧化钼)以及阻燃剂b(硼酸锌、碱式碳酸镁、锡酸硅、锡酸镁、蒙脱土)，阻燃剂a为常规阻燃剂，阻燃剂b为填充型阻燃剂，能赋予材料尺寸稳定性，当然也能赋予碳层稳定性，提高无固相机物含量，提高碳残率；这两类阻燃剂的并用，可以产生协同效应，进一步提高阻燃效率，保持聚合物的力学性能。
4.本发明技术方案使用了两类成碳剂，成碳剂a(苯氧基聚磷腈、六苯氧环三磷腈)为磷氮系阻燃剂(磷腈类阻燃剂)，其磷氮的杂环结构和苯环结构具有较高的磷、氮、碳含量。氮元素在燃烧过程中能够充当气源，使碳层蓬松、膨胀；另一方面，磷元素能够生成焦磷酸盐或者充当酸源，加快成碳速率，碳元素能够增加体系碳含量，提高碳层厚度，减少碳层裂纹；并且此类有机阻燃剂相对无机阻燃剂具有更好的相容性；另一方面，磷腈类阻燃剂和聚苯醚(成碳剂b)共用能形成较厚、致密稳固的碳层，可以有效的促进成碳质量
5.增塑剂是导致PVC可燃，成碳性差的根本原因，原因在于它的气相自由基，挥发导致体积收缩碳层破裂。氢氧化铝对氧指数的提高很明显，这可能是氢氧化铝分解释放的水蒸气，膨胀，同时残留的氧化铝燃烧后容易粉化，不能有效的粘结碳层，导致碳层破裂。氢氧化镁的成碳效果优于氢氧化铝。磷腈类阻燃剂和聚苯醚共用能形成较厚、致密稳固的碳层，可以有效的促进成碳质量。
6.苯氧基聚磷腈、六苯氧环三磷腈，是属于不易挥发的磷氮系阻燃剂，其遵循的凝聚相阻燃剂。磷腈热分解时吸热是冷却机理；其受热分解生成的磷酸、偏磷酸和聚磷酸，可在聚合物材料的表面形成一层不挥发性保护膜，隔绝了空气，这是隔离膜机理；同时受热后放出二氧化碳、氨气、氮气、水蒸汽等气体，这是稀释机理；这些不燃烧的气体阻断了氧的供应，实现了阻燃增效和协同的目的，且聚合物燃烧时有PO·基团形成，它可与火焰区域中的H·、HO·、C·活性基团结合，起到抑制火焰的作用，这是终止链反应机理。对于成碳，其中磷元素抑制熏燃，即：碳的阴燃，其作用机理是碳层表面覆盖有多磷酸、焦磷酸物质和碳上可氧化的活性中心的钝化。氮元素燃烧后释放的气体氮气、氨气等，能够使碳层形成多孔结构，碳层厚度增加，碳层厚度增加的好处为增加火焰与燃烧物的距离，增加增塑剂从内部渗透到外部的距离。聚苯醚的高碳含量结构，可以增加材料中的碳源，增加碳层厚度、密实性，降低碳层可渗透性，减少增塑剂气化、游离氢自由基等可燃物质向表面的扩散，降低表层可燃物浓度。对于氧指数的变化，磷元素会抑制三氧化二锑的阻燃效果，目前发现，高成碳也会抑制三氧化二锑的阻燃效果。这可能是成碳在形成稳固致密的碳层时，会抑制气相三氯化锑的形成，降低气相阻燃效率。但是氧指数30对PVC而言，阻燃已经达到难燃一级，同时氧指数对材料的阻燃的评判具有局限性。
7.磷酸酯、四溴苯酐酯都对氧指数有明显提升、对低温有较大影响、残碳率有略微提升。四溴苯酐酯阻燃机理为气相阻燃机理，主要是捕捉空气中的自由基来实现阻燃。但是溴-碳的键能低于氯-碳键能，更加容易产生溴自由基和溴化氢，同时氯化氢虽然也能大量产生，但是其在火焰前沿的浓度比较低。溴阻燃的效率要高于氯。并且四溴苯酐酯其含有苯环结构，分解的苯环结构能够残留在碳层里面形成焦炭，作为防火屏障。磷酸酯增塑剂，作为挥发性增塑剂是有效的火焰抑制剂。磷酸酯能够裂解成小分子或自由基，他们能吸收火焰区的氢自由基，降低自由基的浓度而使火焰熄灭。对于碳残量略微有影响，可能是苯环残留在碳层中，增加了碳层质量。氧指数降低，是由于三氧化二锑与磷的拮抗作用，但是磷系阻燃剂，其残留物碳含量高，能改善碳层结构，减少碳层炸裂的现象。
8.这里对聚苯醚进行说明，其与PVC的相容性不好，故本文通过低温破碎的方式，将聚苯醚研磨成5-10um的粉末。其以填充的形式，以海岛结构形式分布于基体中。虽然会导致强度伸率降低，但是依然能满足PVC的使用要求例如：GB/T 8815UL1581等.
本发明的优点：
本发明技术方案中所述的电缆料成碳性高，碳层致密、厚实，使PVC的阻燃从阻燃材料迈向防火材料高端市场。此产品能解决目前各类大量含有易燃物质的网络线、高压电力电缆等产品高阻燃要求，目前国内暂时没有发现对手。
本发明技术方案通过使用溴系和磷系阻燃增塑剂替代常规增塑剂，溴系提高气相阻燃机理效率，磷系充当酸源进一步促进成碳速度，减少PVC材料由于增塑剂燃烧所导致的碳层减少、坍塌、滴流情况。并添加一系列高碳低氢含量的成碳剂，使碳层的厚度增加、表面裂纹减少，改善成碳质量。从而使非常柔软的PVC材料能通过各类阻燃测试，例如：V0、VW-1、FT-1、针焰实验等阻燃测试，同时也让PVC电缆的常规阻燃，迈向防火材料，保护电缆火灾中能正常工作。
本发明技术方案同时也解决了常规磷氮阻燃剂，在PVC中成碳质量差，裂纹多，碳层不密实容易炸裂等问题。
总之，本发明通过选择特定的两类增塑剂、两类阻燃剂以及两类成碳剂，通过组合物共同作用效果提供了一种成碳性良好的PVC电缆料。
附图说明
附图1为实施例1的燃烧成碳图和表面裂纹图
附图2为实施例2的燃烧成碳图和表面裂纹图
附图3为实施例3的燃烧成碳图和表面裂纹图
附图4为对比例1的燃烧成碳图
附图5为实施例1和对比例1的燃烧对比图
具体实施方式
下面结合实施例对本发明作进一步描述：
为了更加清楚简洁地描述以下实施例，实施例中一些所涉及的材料采用了其英文代号。
所涉及的英文代号的中文含义分别为：
PVC为聚氯乙烯、TOTM为偏苯三酸三辛酯、DOTP为对苯二甲酸二辛酯、DINP为邻苯二甲酸二异壬酯、SPVC为悬浮聚合聚氯乙烯、EPVC为乳液聚合聚氯乙烯、CPVC为氯化聚氯乙烯、DPOP为磷酸二苯异辛酯。
碳残率测试方法：将产品压制成0.5-0.6mm薄片，取1.5*1.5cm的方形，放置于金属板上，用甲烷燃气正面点燃，火焰需要覆盖整个薄片，最少燃烧3min，直到表面全部碳化，待碳层冷却后，绘制1.5*1.5的白纸方框内，顶部拍照，记录碳层表面状态和记录碳层质量保留率。
实施例1～10：一种成碳性良好的PVC电缆料及其制备方法，其原料配方(单位：重量份)如表1：
表1一种成碳性良好的PVC电缆料实施例1-5组分表
表2实施例中使用的各组分原材料名称：
上述实施例中，偏苯三酸酯选用的是波林TM8-10,亚磷酸酯类稳定剂为磷酸二苯异辛酯(DPOP)、硫代二丙酸双月桂酯(DLTP)，钙锌稳定剂为熊牌8656/9700，聚苯醚选用的是沙特基础工业公司SA9000。
生产工艺按照以下步骤一次进行：原辅材料准备—按照配方比例计量称量—高速捏合—双螺杆挤出机组进行挤出混炼塑化—单螺杆造粒—冷却过筛—保证。捏合工艺使用高速捏合机将原辅材料在高速摩擦下升温至130-140℃，并得到充分的混合均匀和预塑化；双螺杆的设定温度为130—160℃，单螺杆的温度设定为100—130℃，通过双螺杆塑化，单螺杆造粒，冷却后计量包装，即本发明的产品。将本发明的材料在螺杆直径50mm的挤出机生产流水线上，温度设置140—175℃，能得到高成碳PVC护层料，相对普通PVC而言不仅具有良好的柔性同时具有良好的阻燃和成碳性。
普通PVC阻燃护层料的配方与实验结果数据如下：
普通PVC阻燃护层料燃烧配方与结果
以上实施例仅用于对本发明进行说明，并不构成对权利要求范围的限制，本领域技术人员可以想到的其他替代受到，均在权利要求范围内。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。
Claims (8)
1.一种成碳性良好的PVC电缆料，其特征在于：主要由以下重量份数的物质组成：
聚氯乙烯树脂 100份；
增塑剂a 20-40份；
增塑剂b 10-30份；
阻燃剂a 5-15份；
阻燃剂b 5-15份；
成碳剂a 5-15份；
成碳剂b 5-15份；
所述增塑剂a为偏苯三酸酯、对苯二甲酸二辛酯、邻苯二甲酸二异壬酯、植物油酯中的一种或几种；
所述增塑剂b为四溴苯酐酯和/或磷酸酯类增塑剂；
所述阻燃剂a为三氧化二锑、硅酸盐类阻燃剂、三氧化钼中的一种或几种；所述阻燃剂b为硼酸锌、碱式碳酸镁、锡酸硅、锡酸镁、蒙脱土中的一种或几种；
所述成碳剂a为苯氧基聚磷腈和/或六苯氧环三磷腈；成碳剂b为聚苯醚。
2.根据权利要求1所述的电缆料，其特征在于：所述聚氯乙烯树脂包括聚氯乙烯均聚物和/或聚氯乙烯共聚物；所述聚氯乙烯均聚物为悬浮聚合聚氯乙烯、乳液聚合聚氯乙烯、氯化聚氯乙烯；聚氯乙烯共聚物包括氯醋树脂、氯化聚乙烯。
3.根据权利要求1所述的电缆料，其特征在于：还包括10-40份填料a，所述填料a为碳酸钙；10-40份填料b，所述填料b为氢氧化铝、氢氧化镁、滑石粉的一种或几种。
4.根据权利要求1所述的电缆料，其特征在于：还包括2-10份热稳定剂，所述热稳定剂为亚磷酸酯类稳定剂和/或钙锌稳定剂。
5.根据权利要求1所述的电缆料，其特征在于：还包括0.1-2份抗氧剂，所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂1024、抗氧剂1098中的一种或几种。
6.根据权利要求1所述的电缆料，其特征在于：还包括5-10份增韧剂，所述增韧剂为美国杜邦牌号Elvaloy HP441增韧剂、α-甲基苯乙烯-丙烯腈共聚物、氯化聚乙烯中的一种或几种。
7.根据权利要求1所述的电缆料，其特征在于：还包括0.3-2份润滑剂，所述润滑剂为硬脂酸、季戊四醇硬脂酸酯、聚乙烯蜡、硬脂酸钙、氧化聚乙烯中的一种或几种。
8.一种用于权利要求1～7任一项所述一种成碳性良好的PVC电缆料的制备方法，其特征在于，包括以下步骤：
按配方比例计量称重得到原辅材料；将计量称重好的原辅材料放入高速捏合机中高速摩擦下升温至130至140℃进行高速捏合，充分混合均匀和预塑化；放入双螺杆挤出机组130—160℃下进行挤出混炼塑化；100—130℃下单螺杆造粒。
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