CN116199967A - 硅烷交联船用耐油线缆护套料 - Google Patents
硅烷交联船用耐油线缆护套料 Download PDFInfo
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- CN116199967A CN116199967A CN202310299593.5A CN202310299593A CN116199967A CN 116199967 A CN116199967 A CN 116199967A CN 202310299593 A CN202310299593 A CN 202310299593A CN 116199967 A CN116199967 A CN 116199967A
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- 239000000463 material Substances 0.000 title claims abstract description 43
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 20
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 16
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229920001400 block copolymer Polymers 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- 229920001661 Chitosan Polymers 0.000 claims description 93
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 239000003063 flame retardant Substances 0.000 claims description 40
- 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 39
- 238000006243 chemical reaction Methods 0.000 claims description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 24
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 22
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 22
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 14
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- 238000009461 vacuum packaging Methods 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- 229920006228 ethylene acrylate copolymer Polymers 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 4
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000779 smoke Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002341 toxic gas Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical group CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- -1 halogen-free Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- 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
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Abstract
本发明公开了硅烷交联船用耐油线缆护套料,包括A组分和B组分,其特征在于:所述A组分包括如下重量份原料:10‑20份乙烯‑醋酸乙烯共聚物,10‑20份乙烯‑丙烯‑辛稀三元嵌段共聚物,0.5‑1份交联剂,0.1‑0.5份硫化剂等;所述B组分包括如下重量份原料:10‑20份乙烯‑醋酸乙烯共聚物,10‑20份乙烯‑丙烯‑辛稀三元嵌段共聚物,0.5‑1份催化剂等;本发明不需要辐照交联,能够室温下自然交联固化,解决了在不发达地区无辐照设备的应用问题。
Description
技术领域
本发明涉及线缆护套材料技术领域,具体涉及一种硅烷交联船用耐油线缆护套料。
背景技术
近些年来,在船舶、海底、机车等某些特殊场合下使用的电缆要求同时具备低烟、无卤、阻燃和耐油等特性。而传统型的如氯丁橡胶、氯化聚乙烯虽然具有很好的耐油性能,但其在燃烧过程中放出大量的烟雾和有毒气体,对人体会造成危害,同时也会对仪器设备造成腐蚀,因此很难满足人们对环保的要求。
乙烯-醋酸乙烯酯共聚物具有优异的耐油性,此外其在耐高温,耐气候老化(仅次于EPDM)以及阻燃性能方面都非常优秀。然而,为了提高其阻燃性能,往往需要加入大量的阻燃剂,如无机阻燃剂,氢氧化铝、氢氧化镁等,造成材料力学性能下降,而有机膨胀型阻燃剂往往是由小分子组成的,这就导致阻燃剂在应用于其他材料时,随着时间的推移会析出,导致其阻燃效果降低。
发明内容
为了解决上述技术问题,本发明提供一种硅烷交联船用耐油线缆护套料。
本发明的目的可以通过以下技术方案实现:
硅烷交联船用耐油线缆护套料,包括A组分和B组分,其特征在于:所述A组分包括如下重量份原料:10-20份乙烯-醋酸乙烯共聚物,10-20份乙烯-丙烯-辛稀三元嵌段共聚物,4-5份相容剂,25-35份阻燃剂,0.3-0.5份抗氧剂,0.5-1份交联剂,0.1-0.5份硫化剂,1-2份加工助剂;
所述B组分包括如下重量份原料:10-20份乙烯-醋酸乙烯共聚物,10-20份乙烯-丙烯-辛稀三元嵌段共聚物,4-5份相容剂,25-35份阻燃剂,0.3-0.5份抗氧剂,1-2份加工助剂,0.5-1份催化剂。
进一步地:所述A组分和B组分中乙烯-醋酸乙烯共聚物的醋酸乙烯含量为28-70%。
进一步地:所述A组分和B组分中的相容剂为乙烯-马来酸酐接枝物、乙烯-马来酸酐-丙烯酸酯共聚物和乙烯-丙烯酸酯共聚物中的任意一种。
进一步地:所述A组分和B组分中的抗氧剂为受阻酚类抗氧剂。
进一步地:所述A组分中交联剂为乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷和乙烯基三(β-甲氧乙氧基)硅烷中的任意一种。
进一步地:所述A组分和B组分中的加工助剂为硅酮、PE蜡和硬脂酸中的任意一种。
进一步地:所述B组分中的催化剂为螯合锡、二月桂酸二丁基锡和辛酸亚锡中的任意一种。
进一步地:所述A组分和B组分中的阻燃剂包括如下步骤制成:
步骤S1、将改性壳聚糖加入二氯甲烷中,氮气气氛下升温至80℃,加入对苯二酚和三乙胺,保温反应12h,反应结束后旋蒸除去溶剂,干燥,制得接枝壳聚糖;
步骤S1中初改性壳聚糖继续与对苯二酚反应,制备出接枝壳聚糖,反应过程如下所示:
步骤S2、将制得的接枝壳聚糖和环氧氯丙烷混合后升温至110℃,保温1h后降温至65℃,滴加质量分数30%氢氧化钠水溶液,保温反应2h,反应结束后冷却至室温,制得环氧化壳聚糖;
步骤S2中接枝壳聚糖上的酚羟基与环氧氯丙烷反应,在壳聚糖结构上引入环氧基,反应过程如下所示:
步骤S3、将环氧壳聚糖和DOPO加入丙酮中,回流反应2h,反应结束后旋蒸除去丙酮,真空干燥8h,制得阻燃剂。
步骤S3中环氧壳聚糖上的环氧基与DOPO反应,进而将DOPO结构引入壳聚糖中,制备出高阻燃的阻燃剂,反应过程如下所示:
进一步地:步骤S1中控制初改性壳聚糖、对苯二酚、三乙胺和二氯甲烷的用量比为0.5-0.8g∶1-1.5g∶1-1.2g∶5-10mL,步骤S2中控制接枝壳聚糖上的酚羟基和环氧氯丙烷的摩尔比为1∶1,氢氧化钠水溶液的用量为接枝壳聚糖重量的30%,步骤S3中控制环氧壳聚糖上的环氧基与DOPO的摩尔比为1∶1。
进一步地:所述改性壳聚糖包括如下步骤制成:
步骤S11、将壳聚糖加入装有甲烷磺酸的四口烧瓶中,溶胀30mi n后缓慢加入五氧化二磷,通入氮气,冰水浴下匀速搅拌并反应3h,反应结束后用***沉淀,抽滤,分别用丙酮清洗3次,甲醇清洗3次,***清洗1次,清洗结束后在65℃下真空干燥12h,制得初改性壳聚糖,控制壳聚糖、甲烷磺酸和五氧化二磷的用量比为1.5-2.0g∶10-15mL∶1.5-2.0g;
步骤S12、将初改性壳聚糖加入甲苯中,匀速搅拌30mi n后加入二氯亚砜和乙醇,氮气气氛下升温至40℃,匀速搅拌并反应4h,反应结束后分别用甲苯、乙醇洗涤3次,抽滤,真空干燥14h,制得改性壳聚糖,控制初改性壳聚糖、甲苯、二氯亚砜和乙醇的用量比为0.8-1g∶10mL∶0.8-1mL∶2mL。
步骤S11中将壳聚糖用甲烷磺酸溶胀后,加入五氧化二磷,壳聚糖与五氧化二磷反应,制备出初改性壳聚糖,之后步骤S12中初改性壳聚糖与二氯亚砜发生酰氯化反应,制备出改性壳聚糖,该改性壳聚糖结构如下所示:
进一步地:该耐油线缆护套料包括如下步骤制成:
第一步、将A组分中所有物料混匀,在密炼机中塑化15分钟,塑化温度为150℃,塑化完成后放入挤出造粒机中进行造粒,造粒完成后进行真空包装,制得A组分;
第二步、将B组分中所有物料混匀,在密炼机中塑化15分钟,塑化温度为150℃,塑化完成后放入挤出造粒机中进行造粒,造粒完成后进行真空包装,制得B组分。
本发明的有益效果:
本发明通过A、B组分制备出一种硅烷交联船用耐油线缆护套料,加工时将A、B组分混合,其中A组分在加工过程中聚合物树脂在硫化剂作用下发生热解自由基反应,优先失去叔碳原子上的H原子产生自由基,该自由基与乙烯基硅烷的乙烯基反应生成含有三甲氧基或乙氧基硅酯基的接枝聚合物,当与B组分混合后,B组分中的催化剂会使接枝聚合物首先在空气中的水汽作用下发生水解生成硅醇,然后进一步缩合形成Si-O-Si键,从而使聚合物大分子间产生交联,形成三维空间网络结构,本发明不需要辐照交联,能够室温下自然交联固化,解决了在不发达地区无辐照设备的应用问题;
本发明还制备出一种阻燃剂,该阻燃剂以壳聚糖作为基体,壳聚糖作为天然的高分子材料,原料来源广泛,价格低廉,通过对其进行一系列的改性,制备出高分子膨胀型阻燃剂,从结构上看,该阻燃剂引入了磷元素和苯环结构,具有优良的阻燃性能,不含卤族元素,燃烧时不会释放有害气体,而且高含量的苯环结构,燃烧时能够提高炭层的致密度,进一步提高阻燃性。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1:阻燃剂包括如下步骤制成:
将壳聚糖加入装有甲烷磺酸的四口烧瓶中,溶胀30mi n后缓慢加入五氧化二磷,通入氮气,冰水浴下匀速搅拌并反应3h,反应结束后用***沉淀,抽滤,分别用丙酮清洗3次,甲醇清洗3次,***清洗1次,清洗结束后在65℃下真空干燥12h,制得初改性壳聚糖,控制壳聚糖、甲烷磺酸和五氧化二磷的用量比为1.5g∶10mL∶1.5g;
将初改性壳聚糖加入甲苯中,匀速搅拌30mi n后加入二氯亚砜和乙醇,氮气气氛下升温至40℃,匀速搅拌并反应4h,反应结束后分别用甲苯、乙醇洗涤3次,抽滤,真空干燥14h,制得改性壳聚糖,控制初改性壳聚糖、甲苯、二氯亚砜和乙醇的用量比为0.8g∶10mL∶0.8mL∶2mL;
将改性壳聚糖加入二氯甲烷中,氮气气氛下升温至80℃,加入对苯二酚和三乙胺,保温反应12h,反应结束后旋蒸除去溶剂,干燥,制得接枝壳聚糖,控制初改性壳聚糖、对苯二酚、三乙胺和二氯甲烷的用量比为0.5g∶1g∶1g∶5mL;
将制得的接枝壳聚糖和环氧氯丙烷混合后升温至110℃,保温1h后降温至65℃,滴加质量分数30%氢氧化钠水溶液,保温反应2h,反应结束后冷却至室温,制得环氧化壳聚糖,控制接枝壳聚糖上的酚羟基和环氧氯丙烷的摩尔比为1∶1,氢氧化钠水溶液的用量为接枝壳聚糖重量的30%;
将环氧壳聚糖和DOPO加入丙酮中,回流反应2h,反应结束后旋蒸除去丙酮,真空干燥8h,制得阻燃剂,控制环氧壳聚糖上的环氧基与DOPO的摩尔比为1∶1。
实施例2:阻燃剂包括如下步骤制成:
将壳聚糖加入装有甲烷磺酸的四口烧瓶中,溶胀30mi n后缓慢加入五氧化二磷,通入氮气,冰水浴下匀速搅拌并反应3h,反应结束后用***沉淀,抽滤,分别用丙酮清洗3次,甲醇清洗3次,***清洗1次,清洗结束后在65℃下真空干燥12h,制得初改性壳聚糖,控制壳聚糖、甲烷磺酸和五氧化二磷的用量比为1.8g∶12mL∶1.8g;
将初改性壳聚糖加入甲苯中,匀速搅拌30mi n后加入二氯亚砜和乙醇,氮气气氛下升温至40℃,匀速搅拌并反应4h,反应结束后分别用甲苯、乙醇洗涤3次,抽滤,真空干燥14h,制得改性壳聚糖,控制初改性壳聚糖、甲苯、二氯亚砜和乙醇的用量比为0.8g∶10mL∶1mL∶2mL;
将改性壳聚糖加入二氯甲烷中,氮气气氛下升温至80℃,加入对苯二酚和三乙胺,保温反应12h,反应结束后旋蒸除去溶剂,干燥,制得接枝壳聚糖,控制初改性壳聚糖、对苯二酚、三乙胺和二氯甲烷的用量比为0.6g∶1.2g∶1.1g∶8mL;
将制得的接枝壳聚糖和环氧氯丙烷混合后升温至110℃,保温1h后降温至65℃,滴加质量分数30%氢氧化钠水溶液,保温反应2h,反应结束后冷却至室温,制得环氧化壳聚糖,控制接枝壳聚糖上的酚羟基和环氧氯丙烷的摩尔比为1∶1,氢氧化钠水溶液的用量为接枝壳聚糖重量的30%;
将环氧壳聚糖和DOPO加入丙酮中,回流反应2h,反应结束后旋蒸除去丙酮,真空干燥8h,制得阻燃剂,控制环氧壳聚糖上的环氧基与DOPO的摩尔比为1∶1。
实施例3:阻燃剂包括如下步骤制成:
将壳聚糖加入装有甲烷磺酸的四口烧瓶中,溶胀30mi n后缓慢加入五氧化二磷,通入氮气,冰水浴下匀速搅拌并反应3h,反应结束后用***沉淀,抽滤,分别用丙酮清洗3次,甲醇清洗3次,***清洗1次,清洗结束后在65℃下真空干燥12h,制得初改性壳聚糖,控制壳聚糖、甲烷磺酸和五氧化二磷的用量比为2.0g∶15mL∶2.0g;
将初改性壳聚糖加入甲苯中,匀速搅拌30mi n后加入二氯亚砜和乙醇,氮气气氛下升温至40℃,匀速搅拌并反应4h,反应结束后分别用甲苯、乙醇洗涤3次,抽滤,真空干燥14h,制得改性壳聚糖,控制初改性壳聚糖、甲苯、二氯亚砜和乙醇的用量比为1g∶10mL∶1mL∶2mL;
将改性壳聚糖加入二氯甲烷中,氮气气氛下升温至80℃,加入对苯二酚和三乙胺,保温反应12h,反应结束后旋蒸除去溶剂,干燥,制得接枝壳聚糖,控制初改性壳聚糖、对苯二酚、三乙胺和二氯甲烷的用量比为0.8g∶1.5g∶1.2g∶10mL;
将制得的接枝壳聚糖和环氧氯丙烷混合后升温至110℃,保温1h后降温至65℃,滴加质量分数30%氢氧化钠水溶液,保温反应2h,反应结束后冷却至室温,制得环氧化壳聚糖,控制接枝壳聚糖上的酚羟基和环氧氯丙烷的摩尔比为1∶1,氢氧化钠水溶液的用量为接枝壳聚糖重量的30%;
将环氧壳聚糖和DOPO加入丙酮中,回流反应2h,反应结束后旋蒸除去丙酮,真空干燥8h,制得阻燃剂,控制环氧壳聚糖上的环氧基与DOPO的摩尔比为1∶1。
实施例4
硅烷交联船用耐油线缆护套料,包括A组分和B组分,其特征在于:所述A组分包括如下重量份原料:10份乙烯-醋酸乙烯共聚物(乙烯-醋酸乙烯共聚物的醋酸乙烯含量为35%),10份乙烯-丙烯-辛稀三元嵌段共聚物,4份乙烯-马来酸酐接枝物,25份实施例1制备出的阻燃剂,0.3份抗氧剂1010,0.5份乙烯基三乙氧基硅烷,0.1份硫化剂DCP,1份硅酮;
所述B组分包括如下重量份原料:10份乙烯-醋酸乙烯共聚物,10份乙烯-丙烯-辛稀三元嵌段共聚物,4份乙烯-马来酸酐接枝物,25份实施例1制备出的阻燃剂,0.3份抗氧剂1010,1份硅酮,0.5份二月桂酸二丁基锡。
该耐油线缆护套料包括如下步骤制成:
第一步、将A组分中所有物料混匀,在密炼机中塑化15分钟,塑化温度为150℃,塑化完成后放入挤出造粒机中进行造粒,造粒完成后进行真空包装,制得A组分;
第二步、将B组分中所有物料混匀,在密炼机中塑化15分钟,塑化温度为150℃,塑化完成后放入挤出造粒机中进行造粒,造粒完成后进行真空包装,制得B组分;
第三步、实际应用时,将A组分和B组分按照19∶1的比例混合均匀,然后通过塑化挤出机制备成护套料,然后在室温放置3天自然交联固化。
实施例5
硅烷交联船用耐油线缆护套料,包括A组分和B组分,其特征在于:所述A组分包括如下重量份原料:15份乙烯-醋酸乙烯共聚物,15份乙烯-丙烯-辛稀三元嵌段共聚物,4.5份乙烯-马来酸酐-丙烯酸酯共聚物,30份实施例2制备出的阻燃剂,0.4份抗氧剂1035,0.8份乙烯基三甲氧基硅烷,0.3份硫化剂DCP,1.5份PE蜡;
所述B组分包括如下重量份原料:15份乙烯-醋酸乙烯共聚物,15份乙烯-丙烯-辛稀三元嵌段共聚物,4份乙烯-马来酸酐-丙烯酸酯共聚物,30份实施例2制备出的阻燃剂,0.4份抗氧剂1035,1.5份PE蜡,0.8份二月桂酸二丁基锡。
该耐油线缆护套料包括如下步骤制成:
第一步、将A组分中所有物料混匀,在密炼机中塑化15分钟,塑化温度为150℃,塑化完成后放入挤出造粒机中进行造粒,造粒完成后进行真空包装,制得A组分;
第二步、将B组分中所有物料混匀,在密炼机中塑化15分钟,塑化温度为150℃,塑化完成后放入挤出造粒机中进行造粒,造粒完成后进行真空包装,制得B组分;
第三步、实际应用时,将A组分和B组分按照19∶1的比例混合均匀,然后通过塑化挤出机制备成护套料,然后在室温放置4天自然交联固化。
实施例6
硅烷交联船用耐油线缆护套料,包括A组分和B组分,其特征在于:所述A组分包括如下重量份原料:20份乙烯-醋酸乙烯共聚物,20份乙烯-丙烯-辛稀三元嵌段共聚物,5份乙烯-丙烯酸酯共聚物,35份实施例3制备出的阻燃剂,0.5份抗氧剂300,1份乙烯基三(β-甲氧乙氧基)硅烷,0.5份硫化剂DCP,2份硬脂酸;
所述B组分包括如下重量份原料:20份乙烯-醋酸乙烯共聚物,20份乙烯-丙烯-辛稀三元嵌段共聚物,5份乙烯-丙烯酸酯共聚物,35份实施例3制备出的阻燃剂,0.5份抗氧剂300,2份硬脂酸,1份辛酸亚锡。
该耐油线缆护套料包括如下步骤制成:
第一步、将A组分中所有物料混匀,在密炼机中塑化15分钟,塑化温度为150℃,塑化完成后放入挤出造粒机中进行造粒,造粒完成后进行真空包装,制得A组分;
第二步、将B组分中所有物料混匀,在密炼机中塑化15分钟,塑化温度为150℃,塑化完成后放入挤出造粒机中进行造粒,造粒完成后进行真空包装,制得B组分;
第三步、实际应用时,将A组分和B组分按照19∶1的比例混合均匀,然后通过塑化挤出机制备成护套料,然后在室温放置5天自然交联固化。
对比例1:本对比例与实施例4相比,用膨胀型阻燃剂I FR代替本发明阻燃剂。
对比例2:本对比例与实施例4相比,用制备出的改性壳聚糖代替本发明阻燃剂。
对实施例4-实施例6和对比例1-对比例2制备出的护套料的阻燃性能进行检测,结果如下表1所示:
表1
从上表1中能够看出本发明实施例制备出的阻燃剂能够赋予护套料优异的阻燃性能。
对实施例5制备出的线缆护套料的性能进行检测,结果如下表2所示:
表2
以上内容仅仅是对本发明的构思所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (10)
1.硅烷交联船用耐油线缆护套料,包括A组分和B组分,其特征在于:所述A组分包括如下重量份原料:10-20份乙烯-醋酸乙烯共聚物,10-20份乙烯-丙烯-辛稀三元嵌段共聚物,4-5份相容剂,25-35份阻燃剂,0.3-0.5份抗氧剂,0.5-1份交联剂,0.1-0.5份硫化剂,1-2份加工助剂;
所述B组分包括如下重量份原料:10-20份乙烯-醋酸乙烯共聚物,10-20份乙烯-丙烯-辛稀三元嵌段共聚物,4-5份相容剂,25-35份阻燃剂,0.3-0.5份抗氧剂,1-2份加工助剂,0.5-1份催化剂。
2.根据权利要求1所述的硅烷交联船用耐油线缆护套料,其特征在于:所述A组分和B组分中乙烯-醋酸乙烯共聚物的醋酸乙烯含量为28-70%。
3.根据权利要求1所述的硅烷交联船用耐油线缆护套料,其特征在于:所述A组分和B组分中的相容剂为乙烯-马来酸酐接枝物、乙烯-马来酸酐-丙烯酸酯共聚物和乙烯-丙烯酸酯共聚物中的任意一种。
4.根据权利要求1所述的硅烷交联船用耐油线缆护套料,其特征在于:所述A组分和B组分中的抗氧剂为受阻酚类抗氧剂。
5.根据权利要求1所述的硅烷交联船用耐油线缆护套料,其特征在于:所述A组分中交联剂为乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷和乙烯基三(β-甲氧乙氧基)硅烷中的任意一种。
6.根据权利要求1所述的硅烷交联船用耐油线缆护套料,其特征在于:所述A组分和B组分中的加工助剂为硅酮、PE蜡和硬脂酸中的任意一种。
7.根据权利要求1所述的硅烷交联船用耐油线缆护套料,其特征在于:所述B组分中的催化剂为螯合锡、二月桂酸二丁基锡和辛酸亚锡中的任意一种。
8.根据权利要求1所述的硅烷交联船用耐油线缆护套料,其特征在于:所述A组分和B组分中的阻燃剂包括如下步骤制成:
步骤S1、将改性壳聚糖加入二氯甲烷中,氮气气氛下升温至80℃,加入对苯二酚和三乙胺,保温反应12h,反应结束后旋蒸,干燥,制得接枝壳聚糖,控制初改性壳聚糖、对苯二酚、三乙胺和二氯甲烷的用量比为0.5-0.8g∶1-1.5g∶1-1.2g∶5-10mL;
步骤S2、将制得的接枝壳聚糖和环氧氯丙烷混合后升温至110℃,保温1h后降温至65℃,滴加质量分数30%氢氧化钠水溶液,保温反应2h,反应结束后冷却至室温,制得环氧化壳聚糖,控制接枝壳聚糖上的酚羟基和环氧氯丙烷的摩尔比为1∶1,氢氧化钠水溶液的用量为接枝壳聚糖重量的30%;
步骤S3、将环氧壳聚糖和DOPO加入丙酮中,回流反应2h,反应结束后旋蒸,真空干燥8h,制得阻燃剂,控制环氧壳聚糖上的环氧基与DOPO的摩尔比为1∶1。
9.根据权利要求8所述的硅烷交联船用耐油线缆护套料,其特征在于:所述改性壳聚糖包括如下步骤制成:
步骤S11、将壳聚糖加入装有甲烷磺酸的四口烧瓶中,溶胀30min后缓慢加入五氧化二磷,通入氮气,冰水浴下匀速搅拌并反应3h,反应结束后用***沉淀,抽滤,分别用丙酮清洗3次,甲醇清洗3次,***清洗1次,清洗结束后在65℃下真空干燥12h,制得初改性壳聚糖,控制壳聚糖、甲烷磺酸和五氧化二磷的用量比为1.5-2.0g∶10-15mL∶1.5-2.0g;
步骤S12、将初改性壳聚糖加入甲苯中,匀速搅拌30min后加入二氯亚砜和乙醇,氮气气氛下升温至40℃,匀速搅拌并反应4h,反应结束后分别用甲苯、乙醇洗涤3次,抽滤,真空干燥14h,制得改性壳聚糖,控制初改性壳聚糖、甲苯、二氯亚砜和乙醇的用量比为0.8-1g∶10mL∶0.8-1mL∶2mL。
10.根据权利要求1所述的硅烷交联船用耐油线缆护套料,其特征在于:该耐油线缆护套料包括如下步骤制成:
第一步、将A组分中所有物料混匀,在密炼机中塑化15分钟,塑化温度为150℃,塑化完成后放入挤出造粒机中进行造粒,造粒完成后进行真空包装,制得A组分;
第二步、将B组分中所有物料混匀,在密炼机中塑化15分钟,塑化温度为150℃,塑化完成后放入挤出造粒机中进行造粒,造粒完成后进行真空包装,制得B组分。
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