CN115521419A - 一种改性木质素磺酸钙热塑性弹性体材料及其制备方法 - Google Patents
一种改性木质素磺酸钙热塑性弹性体材料及其制备方法 Download PDFInfo
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- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical class [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims abstract description 30
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 239000000839 emulsion Substances 0.000 claims abstract description 40
- 229920005551 calcium lignosulfonate Polymers 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 8
- 239000006172 buffering agent Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 31
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 26
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
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- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
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- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 102000016938 Catalase Human genes 0.000 claims description 2
- 108010053835 Catalase Proteins 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 108010029541 Laccase Proteins 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940101006 anhydrous sodium sulfite Drugs 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
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- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 2
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- 229920005610 lignin Polymers 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- -1 alkyl dimethyl benzyl quaternary ammonium salt Chemical class 0.000 description 6
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 6
- 229910001626 barium chloride Inorganic materials 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
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- 229920001971 elastomer Polymers 0.000 description 4
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- 150000003254 radicals Chemical class 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- 238000007031 hydroxymethylation reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940045511 barium chloride Drugs 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
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- 235000011176 polyphosphates Nutrition 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
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- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
本发明公开了一种改性木质素磺酸钙热塑性弹性体材料及其制备方法,包括:1)配置单体乳液:取乳化剂溶于水中,同时加入接枝单体和氧化剂于乳化剂溶液中用玻璃棒搅拌均匀;2)配置木质素磺酸钙溶液;3)制备种子乳液:取单体乳液于三口烧瓶中,同时加入缓冲剂调节溶液pH值;4)由步骤3)制备的种子乳液变透明并出现蓝色荧光时,开始缓慢匀速加入剩余单体乳液和CLS溶液,同时升高温度;5)加入所有反应物后升温反应,得改性CLS乳液;6)加破乳剂破乳,离心烘干即得接枝产物。7)产物后处理,得到改性木质素磺酸钙热塑性弹性体材料。本发明在降低全降解材料成本的同时,又能提高耐水性、阻隔性和热稳定性等性能。
Description
技术领域
本发明涉及生物降解材料领域,具体涉及一种改性木质素磺酸钙热塑性弹性体材料及其制备方法,一定程度上拓宽了TPS的使用范围,同时大大提高了木质素(LS)的利用率。
背景技术
木质素与纤维素、半纤维素一起组成植物的木质结构,主要存在于细胞壁中起支撑和保护的作用。木质素是自然界中唯一含芳环的天然高分子,其结构中官能团种类丰富,储量巨大,具有代替石油的潜力。木质素是热塑性天然高分子,具有高抗冲击强度、良好的耐热性、耐水性和廉价易得等优点。用木质素作为填料与其他生物降解高分子材料共混制备出的生物全降解材料,在降低全降解材料成本的同时,又能提高复合材料的耐水性、阻隔性和热稳定性等性能。
木质素磺酸钙是木质素的衍生物,其改性制备表面活性剂近年来蓬勃发展并取得了系列重要进展,改性产品广泛地用于工农业生产。其分子结构基本保留了木质素的结构特征,即苯丙烷单元结构和大量醚键连接结构,其侧链上还引入了大量的磺酸盐基团,而它带有的磺酸基团又使得它拥有能溶于水的特性。其分子中含有的大量的活性基团,可以通过氧化、接枝、胺化、缩聚、羟甲基化等化学方法来改性,包括羟甲基化改性、氧化改性、接枝共聚改性和复合改性等,都可以制备出具有不同理化性质和用途的聚合物。
热塑性弹性体(TPE)是一种兼具橡胶和塑料性能的高分子材料,具体表现为在常温下呈现橡胶弹性,而在高温下又能够加工进行塑化成型。TPE具备传统交联硫化橡胶的高弹性、耐老化、耐油性各项优异性能,同时又具备普通塑料加工方便、加工方式广的特点。可采用注塑、挤出、吹塑等加工方式生产,水口边角粉碎后100%直接二次使用,既简化加工过程,又降低加工成本,因此热塑性弹性体材料已成为能够取代传统橡胶的新型材料。目前热塑性弹性体材料主要应用于电线电缆、厨房用品、婴儿产品、运动器材等领域。本发明是一种基于木质素磺酸钙,通过化学接枝得到的生物全降解的热塑性弹性体材料。
发明内容
本发明的目的在于提供一种改性木质素磺酸钙热塑性弹性体材料及其制备方法,解决了CLS(木质素磺酸钙)加工过程中易分解的问题,且成本低廉,原料丰富,符合可持续发展的理念。
一种改性木质素磺酸钙热塑性弹性体材料的制备方法,包括以下步骤:
1)配置单体乳液:取0.3~3g乳化剂溶于2~20g水中,同时加入10~60g接枝单体和0.1~0.5g氧化引发剂于乳化剂溶液中用玻璃棒搅拌均匀;
2)配置木质素磺酸钙溶液:取5~40gCLS和0.1~0.5g还原引发剂溶于10~50ml水中搅拌至完全溶解;
3)制备种子乳液:取10~20ml单体乳液于三口烧瓶中,同时加入0.1~0.5g缓冲剂调节溶液pH值,用恒温加热磁力搅拌器搅拌,升温至55~60℃时停止加热;
4))由3)制备的种子乳液变透明并出现蓝色荧光时,开始缓慢匀速加入剩余单体乳液和CLS溶液,每加入1~10ml CLS溶液的同时加入2~8ml单体乳液,在2~3小时内添加完单体,同时升高温度至70~80℃;
5)加入所有反应物后升温至85~90℃反应3~5h后冷却,得改性CLS乳液;
6)加浓度为2~5%的破乳剂破乳,以5000~8000r/min的转速离心分离10~30min,将上层清液分离,下层固体物质在60~80℃下烘干即得接枝产物。
7)产物后处理:将烘干后的产物低温下冷冻后破碎,通过索氏提取器去除产物中未反应的单体,提取器圆底烧瓶中的溶剂为水,抽提时间为5~24h,烘干,得到改性木质素磺酸钙热塑性弹性体材料。
优选地,所述的乳化剂为Tween60、Tween80、Span60、Span80、SDBS、PEG、OP-4、OP-7、OP-10、OP-15、OP-20的一种或几种混合。
优选地,所述的接枝单体为丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸己酯、烯丙基聚乙二醇、马来酸酐和丙烯酰氯中的一种或几种混合。
优选地,所述的氧化-还原引发剂为叔丁基过氧化氢/亚硫酸氢钠、过硫酸铵/亚硫酸氢钠、过硫酸钾/无水亚硫酸钠、过氧化氢/抗坏血酸、过硫酸钾/抗坏血酸、过硫酸铵/硫酸亚铁、亚铁离子与过氧化氢中的一种,或酚型过氧化氢酶,漆酶。
优选地,所述的破乳剂为阴离子破乳剂(十二烷基苯磺酸钠、硬脂酸钠、月桂醇硫酸酯钠、月桂醇聚醚硫酸酯钠、氯化钡等)、阳离子破乳剂(烷基三甲基季铵盐、烷基二甲基苄基季铵盐、烷基二甲基羟乙基季铵盐)、两性破乳剂(嵌段聚醚、烷基酚醛树脂嵌段聚醚、酚胺醛树脂嵌段聚醚、聚磷酸酯等)、SP型(主要组分为聚氧乙烯聚氧丙烯十八醇醚)、AP型(以多乙烯多胺为引发剂的聚氧乙烯聚氧丙烯聚醚)、AE型(以多乙烯多胺为引发剂的聚氧乙烯聚氧丙烯聚醚)一种或几种混合。
本发明采用自由基聚合方式,所选方法为种子乳液聚合,利用氧化-还原引发体系发生氧化还原反应产生初级自由基,反应分为链引发,链增长,链终止三个阶段,链引发阶段THP和NaHSO3发生氧化还原反应产生HSO3 -和(CH3)3CO-,LS中活性基团与HSO3 -反应产生单体自由基引发聚合,链增长阶段烯丙基单体逐步聚合至单体自由基上增加LS分子量及其分布,单体自由基与聚合物碰撞发生链终止反应结束聚合。此外,聚合过程中会发生烯丙基单体自聚以及LS的缩聚反应影响接枝产物的纯度以及接枝率。
与现有技术相比,本发明的优点在于:目前LS广泛应用于混凝土减水剂,助磨剂,粘合剂以及络合金属离子等领域,对其热稳定性的研究很少。本发明的改性木质素磺酸钙热塑性弹性体材料,将CLS改性产物用于热稳定剂,解决了CLS加工过程中易分解的问题,且成本低廉,原料丰富,符合可持续发展的理念。
附图说明
图1为实施例1制备的CLS接枝产物的红外谱图;
图2为CLS和实施例1制备的CLS-g-MA差式扫描量热分析曲线图,a为CLS;b为CLS-g-MA;CLS-g-MA代表MA接枝到CLS上。
具体实施方式
为更好的理解本发明,下面的实施例是对本发明的进一步说明,但本发明的内容不仅仅局限于下面的实施例。
实施例1
1)取0.5g乳化剂op-10溶于15g水中,同时加40g MA(甲基丙烯酸)和0.2g THP(叔丁基过氧化氢)于乳化剂溶液中用玻璃棒搅拌均匀;取8g CLS和0.23g NaHSO3溶于30ml水中搅拌至完全溶解;
2)取10ml单体乳液于三口烧瓶中,同时加入0.5g十二水合磷酸氢二钠调节溶液pH值,用恒温加热磁力搅拌器搅拌,升温至60℃时停止加热;
3)溶液变透明并出现蓝色荧光时开始缓慢匀速加入剩余单体乳液和CLS溶液,每加入1ml CLS溶液的同时加入2ml单体乳液,在3小时内添加完单体,同时升高温度至75℃;加入所有反应物后升温至90℃反应3h后冷却,得改性CLS乳液;
4)加浓度为4%的氯化钡溶液破乳,以8000r/min的转速离心分离30min,将上层清液分离,下层固体物质在60℃下烘干即得接枝产物;
5)将烘干后的产物低温下冷冻后破碎,通过索氏提取器去除产物中未反应的单体,提取器圆底烧瓶中的溶剂为水,抽提时间为5h,烘干,得到改性木质素磺酸钙热塑性弹性体材料。
实施例2
1)取0.8g乳化剂op-10溶于16g水中,同时加16g MA(丙烯酸甲酯)和0.2g THP(叔丁基过氧化氢)于乳化剂溶液中用玻璃棒搅拌均匀;取32g CLS和0.23g NaHSO3溶于30ml水中搅拌至完全溶解;
2)取10ml单体乳液于三口烧瓶中,同时加入0.5g十二水合磷酸氢二钠调节溶液pH值,用恒温加热磁力搅拌器搅拌,升温至60℃时停止加热;
3)溶液变透明并出现蓝色荧光时开始缓慢匀速加入剩余单体乳液和CLS溶液,每加入1ml CLS溶液的同时加入2ml单体乳液,在3小时内添加完单体,同时升高温度至75℃;加入所有反应物后升温至90℃反应3h后冷却,得改性CLS乳液;
4)加浓度为4%的氯化钡溶液破乳,以8000r/min的转速离心分离30min,将上层清液分离,下层固体物质在60℃下烘干即得接枝产物;
5)将烘干后的产物低温下冷冻后破碎,通过索氏提取器去除产物中未反应的单体,提取器圆底烧瓶中的溶剂为水,抽提时间为5h,烘干,得到改性木质素磺酸钙热塑性弹性体材料。
实施例3
1)取0.9g乳化剂op-10溶于12g水中,同时加32g MA(丙烯酸甲酯)和0.2g THP(叔丁基过氧化氢)于乳化剂溶液中用玻璃棒搅拌均匀;取16g CLS和0.23g NaHSO3溶于30ml水中搅拌至完全溶解;
2)取10ml单体乳液于三口烧瓶中,同时加入0.5g十二水合磷酸氢二钠调节溶液pH值,用恒温加热磁力搅拌器搅拌,升温至60℃时停止加热;
3)溶液变透明并出现蓝色荧光时开始缓慢匀速加入剩余单体乳液和CLS溶液,每加入1ml CLS溶液的同时加入2ml单体乳液,在3小时内添加完单体,同时升高温度至75℃;加入所有反应物后升温至90℃反应5h后冷却,得改性CLS乳液;
4)加浓度为4%的氯化钡溶液破乳,以8000r/min的转速离心分离30min,将上层清液分离,下层固体物质在60℃下烘干即得接枝产物。
5)将烘干后的产物低温下冷冻后破碎,通过索氏提取器去除产物中未反应的单体,提取器圆底烧瓶中的溶剂为水,抽提时间为5h,烘干,得到改性木质素磺酸钙热塑性弹性体材料。
实施例4
1)取2.65g乳化剂op-10溶于52g水中,同时加52g MA(丙烯酸甲酯)和0.2g THP(叔丁基过氧化氢)于乳化剂溶液中用玻璃棒搅拌均匀;取7.43g CLS和0.23g NaHSO3溶于30ml水中搅拌至完全溶解;
2)取10ml单体乳液于三口烧瓶中,同时加入0.5g十二水合磷酸氢二钠调节溶液pH值,用恒温加热磁力搅拌器搅拌,升温至60℃时停止加热;
3)溶液变透明并出现蓝色荧光时开始缓慢匀速加入剩余单体乳液和CLS溶液,每加入1ml CLS溶液的同时加入2ml单体乳液,在3小时内添加完单体,同时升高温度至75℃;加入所有反应物后升温至90℃反应3h后冷却,得改性CLS乳液;
4)加浓度为4%的氯化钡溶液破乳,以8000r/min的转速离心分离30min,将上层清液分离,下层固体物质在60℃下烘干即得接枝产物。
5)将烘干后的产物低温下冷冻后破碎,通过索氏提取器去除产物中未反应的单体,提取器圆底烧瓶中的溶剂为水,抽提时间为5h。,烘干,得到改性木质素磺酸钙热塑性弹性体材料。
实施例5
1)取1.92g乳化剂op-10溶于38.5g水中,同时加38.5MA(丙烯酸甲酯)和0.2g THP(叔丁基过氧化氢)于乳化剂溶液中用玻璃棒搅拌均匀;取9.6g CLS和0.23g NaHSO3溶于30ml水中搅拌至完全溶解;
2)取10ml单体乳液于三口烧瓶中,同时加入0.5g十二水合磷酸氢二钠调节溶液pH值,用恒温加热磁力搅拌器搅拌,升温至60℃时停止加热;
3)溶液变透明并出现蓝色荧光时开始缓慢匀速加入剩余单体乳液和CLS溶液,每加入1ml CLS溶液的同时加入2ml单体乳液,在3小时内添加完单体,同时升高温度至75℃;加入所有反应物后升温至90℃反应5h后冷却,得改性CLS乳液;
4)加浓度为4%的氯化钡溶液破乳,以8000r/min的转速离心分离30min,将上层清液分离,下层固体物质在60℃下烘干即得接枝产物;
5)将烘干后的产物低温下冷冻后破碎,通过索氏提取器去除产物中未反应的单体,提取器圆底烧瓶中的溶剂为水,抽提时间为5h,烘干,得到改性木质素磺酸钙热塑性弹性体材料。
图1为实施例1制备的CLS接枝产物的红外谱图,由图中可知,在3435.37cm-1处存在酚羟基H-O的伸缩振动,但吸收峰强度大大减弱,1043.28cm-1处为苯环振动吸收峰,758.36cm-1和825.96cm-1处吸收峰代表苯环的邻对位取代;1725.33cm-1处为羰基C=O的特征吸收峰,结合1194.12cm-1处C-O振动峰证明分子中存在酯基,1194.12cm-1和1156.04cm-1处双重峰进一步证明聚丙烯酸甲酯(Polymethyl Acrylate,简称PMA)存在;2953.62cm-1、2848.82cm-1分别代表甲基和亚甲基C-H的伸缩振动,含氧基团的引入导致其吸收峰变宽且强度减弱,1378.04cm-1、1435.5cm-1分别表示甲基和亚甲基弯曲振动。综上分析可知,接枝产物具有部分CLS以及PMA的特征吸收峰,说明MA成功接枝到CLS上。
图2为CLS和实施例1制备的CLS-g-MA差式扫描量热分析曲线,由图可知,CLS的Tg为104℃,通过查阅相关资料得知丙烯酸甲酯均聚物的Tg为9℃。在图中b曲线中9~104℃温度范围内仅有一个吸热峰,即接枝产物的Tg为25℃,且MA分子链段与CLS完全相容,也更有力的证明了单体MA成功接枝到CLS上。
以上所述是本发明的优选实施方式而已,当然不能以此来限定本发明之权利范围,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和变动,这些改进和变动也视为本发明的保护范围。
Claims (6)
1.一种改性木质素磺酸钙热塑性弹性体材料的制备方法,其特征在于,包括以下步骤:
1)配置单体乳液:取0.3~3g乳化剂溶于2~20g水中,同时加入10~60g接枝单体和0.1~0.5g氧化引发剂于乳化剂溶液中用玻璃棒搅拌均匀;
2)配置木质素磺酸钙溶液:取5~40gCLS和0.1~0.5g还原引发剂溶于10~50ml水中搅拌至完全溶解;
3)制备种子乳液:取10~20ml单体乳液于三口烧瓶中,同时加入0.1~0.5g缓冲剂调节溶液pH值,用恒温加热磁力搅拌器搅拌,升温至55~60℃时停止加热;
4)由步骤3)制备的种子乳液变透明并出现蓝色荧光时,开始缓慢匀速加入剩余单体乳液和CLS溶液,每加入1~10ml CLS溶液的同时加入2~8ml单体乳液,在2~3小时内添加完单体,同时升高温度至70~80℃;
5)加入所有反应物后升温至85~90℃反应3~5h后冷却,得改性CLS乳液;
6)加浓度为2~5%的破乳剂破乳,以5000~8000r/min的转速离心分离10~30min,将上层清液分离,下层固体物质在60~80℃下烘干即得接枝产物。
7)产物后处理:将烘干后的产物低温下冷冻后破碎,通过索氏提取器去除产物中未反应的单体,提取器圆底烧瓶中的溶剂为水,抽提时间为5~24h,烘干,得到改性木质素磺酸钙热塑性弹性体材料。
2.根据权利要求1所述的改性木质素磺酸钙热塑性弹性体材料的制备方法,其特征在于,所述的乳化剂为Tween60、Tween80、Span60、Span80、SDBS、PEG、OP-4、OP-7、OP-10、OP-15、OP-20的一种或几种混合。
3.根据权利要求1所述的改性木质素磺酸钙热塑性弹性体材料的制备方法,其特征在于,所述的接枝单体为丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸己酯、烯丙基聚乙二醇、马来酸酐和丙烯酰氯中的一种或几种混合。
4.根据权利要求1所述的改性木质素磺酸钙热塑性弹性体材料的制备方法,其特征在于,所述的氧化-还原引发剂为叔丁基过氧化氢/亚硝酸氢钠、过硫酸铵/亚硫酸氢钠、过硫酸钾/无水亚硫酸钠、过氧化氢/抗坏血酸、过硫酸钾/抗坏血酸、过硫酸铵/硫酸亚铁、亚铁离子与过氧化氢中的一种,或酚型过氧化氢酶,漆酶。
5.根据权利要求1所述的改性木质素磺酸钙热塑性弹性体材料的制备方法,其特征在于,所述的破乳剂为阴离子破乳剂、阳离子破乳剂、两性破乳剂、SP型、AP型、AE型一种或几种混合。
6.一种根据权利要求1-5中任一所述的改性木质素磺酸钙热塑性弹性体材料的制备方法制备的改性木质素磺酸钙热塑性弹性体材料。
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