Shanghai Daoqin Plastics Co., Ltd.

        本文 using/adopting reaction type increase agent —— oxidation 二异丙苯(DCP) and thermoplastic property aldehyde resin (HY-2045), through melt blending method made high density polyethylene (PE) (HDPE)/ waste 旧轮胎胶 powder (GTR) thermoplastic property 硫化胶. through outer absorption light analysis, 差示扫描 amount hot testing, X-射线衍射 analysis and force property can testing and other table/sheet methods, research DCP and HY-2045 for blending material crystallization property can effect/influence. research 结果显示, DCP and HY-2045 add 入, make HDPE/GTR blending material crystallization degree reduce, and blending material crystallization degree HY-2045 content increase 而不断 reduce. another, increase solvent agent HY-2045 content increase, blending material low temperature 区 橡胶 versus 玻璃化转变峰 in 不断拓 wide, high temperature 区 松弛转变峰也变 越 越 obvious.

         front 言

         will waste 旧轮胎胶 powder (GTR) and HDPE through melt blending can made thermoplastic property 硫化胶[1, 2], in certain types degree upper, can achieve waste 旧轮胎 high value recycling utilizing, also tool has very good environmental protection 意义. is, 鉴于HDPE and GTR is versus 容 两 types high poly material, will 二者熔 melt blending made tool has use value thermoplastic property 硫化胶, improvement blending system versus property. generally, in blending system in add tool has and upper types high poly material versus structure copolymer or grafting copolymer [3], can significantly improvement system versus property;当然, can through add reaction type increase agent, oxidation material [4]以 and aldehyde resin [5, 6] and other, improve/increase blending material versus property. however, reaction type increase agent, 如DCP, BIM and other and other, in improvement blending material versus property, improve/increase its force property can meanwhile, for blending material crystallization property can also has different negative effect/influence, this also in 一定程 degree upper effect/influence blending material force property can. according to front research formed 果[7], amount increase agent content make blending material force property can has decline, can can is due to blending material crystallization degree in increase property reaction function lower decline 导致.

         therefore, to DCP and HY-2045会引发 blending material in HDPE基体 versus crosslinked phenomenon and versus interface chemical crosslinked reaction, significantly effect/influence blending material crystallization property can, specific through 差示扫描 amount hot and X射线衍射仪 analysis increase agent for blending material crystallization property can effect/influence. meanwhile, through outer analysis and force property can and other analysis, research increase agent for blending material crystallization property can and high temperature 区松弛转变 effect/influence.

        实验部 separation

        1.实验 raw materials

         high density polyethylene (PE) (HDPE), 5000S, melt flow index is 1.0 g/10min, China 石油兰州石化 company; waste 旧轮胎胶 powder (GTR), 60目, normal temperature powder 碎, as 市弘瑞橡胶 has responsibility company; oxidation 二异丙苯 (DCP), chemical pure, its structure 式如图1 示, Shanghai 白鸽农药化 factory; thermoplastic property aldehyde resin, HY-2045, 羟甲基 content 10.0~14.0%, its structure 式如图1 示, chemical industry research.

        2. HDPE/GTR made process

table/sheet 1 实验 formulation

        GTR in use front need in 80℃ true drying in drying 12 h, remove water separation and other can property material 质. will machine rise temperature setting temperature degree 180℃, high density polyethylene (PE) add 入转矩流变仪 inner, melt 2min, rear add waste powder, 继续熔 melt blending 6min, add thermoplastic property aldehyde resin (HY-2045), melt blending 5 min, most rear add oxidation 二异丙苯 (DCP), specific formulation table/sheet 1, melt blending to 搅拌扭矩 balanced rear material, process large need 14min;然 rear in sheet/plate machine upper pressure made molding, temperature degree is 180℃, pressure is 10MPa, time is 8min. rear in room temperature lower cold pressure 5min, pressure is 10 MPa. rear made strip/profile related property can testing.

        3. property can testing

        (1) outer testing

         will true dry HDPE/GTR blending material pressure made formed surface light slip thin sheet/slice, rear in 布鲁克 optical device company TENSOR-27 type outer upper 进行衰 decrease full 反射红 outer 实验.

        (2) 差示扫描 amount hot testing

         will Sample product abrasion formed powder 状, true drying 12h rear cooling room temperature, 称取约5 mg sample 进行DSC testing, in nitrogen gas lower 以10 k/min rise temperature speed rate from 25℃ rise 至210℃, rear maintain 10 min以消 remove hot history, again 以5 k/min drop room temperature. blending material crystallization degree can according to below/following 公式求:

        (3) X-射线衍射 analysis

        HDPE/GTR blending Sample crystallization degree use TD3500 type X-射线衍射仪 测 amount, scope/range is 5~50°, 扫描精 degree is 0.08 °/s, as electrical pressure is 35 kV, electrical is 25 mA.

        (4) property can analysis

         in METTLER TOLEDO company SDTA861e type force analysis upper for Sample action force property can testing. testing conditions is: rise temperature speed rate 3 k/min, temperature degree scope/range is -80℃~150℃, 实验模式 is tensile 模式, Sample dimensions is 20×9×4, frequency rate 1Hz, 应变 0.1%.

        结果 and 讨论

        1.红 outer light analysis

         in polyethylene (PE) outer in, 1460 cm-1 and 720 cm-1处 absorption is 亚甲基 面 inner 剪式振动 and 摇摆振动 absorption 峰, due to to crystallization effect/influence, HDPE谱图 in upper 述两处 absorption 峰发生 裂缝, formed absorption 峰, separation is 1470, 1460, 730 and 720 cm-1处 absorption 峰, its in, 1470 and 730 cm-1处 absorption is belt/tape absorption 峰, 1460 and 720 cm-1处 absorption is non belt/tape absorption 峰, 1470 and 1460 cm-1处以 and 730 and 720 cm-1处 absorption versus for ratio can reaction HDPE crystallization degree versus for 变化, 且730 and 720 cm-1处 absorption versus for ratio for crystallization degree reaction more add 准确一, crystallization degree in 一定程 degree upper effect/influence material force property can, retardant property can and other physical properties [8].

DCP/HY-2045 quality ratio (phr/phr) separation is, a: 0/0;b: 0.3/0;c: 0.3/4.0;e: 0.3/12.0;g: 0.3/20.0

         therefore, can through comparison 730 and 720cm-1处 absorption 峰 面积 ratio reaction HDPE/GTR crystallization degree 变化, from research increase agent types type and increase agent HY-2045 content for its force property can effect/influence. through 卷积化处理, HDPE/GTR blending material versus for crystallization degree, specific 结果如图2 示. in, 710 cm-1处 absorption is blending material in ring upper C-H键 振动 absorption 峰, its for blending material crystallization degree has effect/influence, 730 and 720 cm-1处 absorption 峰 面积以 and according to its ratio value versus for crystallization degree table/sheet 2 示. from table/sheet in can, increase agent DCP add 入, make blending material crystallization degree reduce, blending material crystallization degree HY-2045 content increase 而不断 decline, this can can is due to reaction type increase agent HY-2045 make blending material interface generate chemical crosslinked, reduce versus HDPE靠近 dispersion versus separation separation active property, another, DCP引发HDPE separation between 发生自 crosslinked, make separation active property decline, from make HDPE/GTR blending material in cooling molding process in, HDPE in 排入晶区 separation 子链段数 amount decrease/reduce, crystallization degree reduce, crystallization 不完善.

注: the DCP/HY-2045 (phr/phr), a: 0/0; b: 0.30/0; c: 0.30/4.00; e: 0.30/12.00; g: 0.30/20.00

        2. crystallization property can analysis

         in upper blending material outer light analysis separation in, 我们提 to increase agent types type and content for HDPE/GTR blending material crystallization degree has effect/influence, crystallization degree and material force property can between also has 密切 联系, usually crystallization degree increase, polymer strong/high degree, tensile modulus and hardness and other improve/increase, fracture elongation 反而会 reduce. therefore, through research different increase system made HDPE/GTR blending material crystallization degree, can increase system and blending material crystallization degree between 关系, comprehensive different increase system for blending material force property can effect/influence. 图3 and 图4 separation is using/adopting DSC and XRD table/sheet 征手段 testing blending material melt 曲线, cooling crystallization 曲线以 and X射线衍射图谱.

         is more add 清晰说明 different increase system for HDPE/GTR blending material crystallization property can effect/influence, 本文添 add pure HDPE melt and cooling crystallization 曲线. polymer crystallization degree according to 公式1计算 to, table/sheet 3 示, from table/sheet in can, increase agent DCP and HY-2045 add 入, make blending material crystallization degree significantly reduce, especially is DCP and HY-2045共同 increase 容时, crystallization degree from 31.86% drop to 15.86%; another, increase agent for blending material crystallization temperature degree and melt temperature degree effect/influence is very obvious. GTR pellets add make HDPE separation active property reduce, crystallization temperature degree versus for rise high, due to crystallization degree reduce, its melt temperature degree reduce. DCP add rear, large separation hot separation understanding generate grade 自由基引发 橡塑 interface chemical crosslinked reaction, less separation HDPE crosslinked, make blending material crystallization degree relatively increase blending material crystallization degree low, melt temperature degree 也随之 reduce. however crystallization temperature degree in reduce, this can can is due to crosslinked HDPE存 in a small amount of crosslinked in blending material cooling crystallization process in provide nucleating agent function, make its crystallization temperature degree has reduce [9]. use DCP and HY-2045共同 increase 容HDPE/GTR blending material 时, due to add HY-2045 make interface separation interface chemical increase function, 当DCP add rear, its hot separation understanding grade 自由基 versus for relatively more HDPE crosslinked reaction, make its crystallization temperature degree relatively DCP mono increase blending material has rise high, melt temperature degree basic maintain 不变. from 图3 in can, HDPE and blending material X射线衍射曲线 in 21.5° and 23.8°出现 两 obvious 衍射峰, separation table/sheet HDPE晶胞 110面 and 200面[10], can 见, GTR and reaction type increase agent add 入, has blending material in HDPE type, this and 文献[11, 12] to 结果一致.

         another, using/adopting XRD testing blending material crystallization degree need high 于DSC testing crystallization degree, is trend and DSC testing versus 一致, increase rear blending material crystallization degree in reduce, type maintain 不变, still is positive 交晶系. HDPE/GTR blending material 经原位 interface chemical increase rear, crystallization degree in reduce.

        3.动态 force property can analysis

        当 Sample to cycle outer force function 时, generate 一定 响应, research types 响应随 temperature degree and function force frequency rate process, is force analysis (dynamical mechanical analysis, DMA). in testing polymer upper 述响应 process in, can to polymer can modulus (E′)以 and loss consumption modulus (E″)随 temperature degree and frequency rate 变化而变化 related 信息, rear through E″ and E′ ratio value, can loss consumption positive value, can to polymer 主转变, grade and other important 信息, 以此推断 blending polymer versus property.

         for/regarding blending material, especially is 本实验 in research HDPE/GTR thermoplastic property 硫化胶, through its force property can testing, can to its versus 玻璃化转变 temperature degree and temperature and other 信息, can reaction type increase agent DCP and HY-2045 for its in high temperature lower 松弛转变 effect/influence, from is interface chemical increase 容HDPE/GTR blending material provide evaluation 信息.

DCP/HY-2045 quality ratio (phr/phr), a: 0/0; b: 0.30/0; c: 0.30/4.00; e: 0.30/12.00; g: 0.30/20.00

        图5 is different increase agent and different content HY-2045 increase HDPE/GTR blending material can modulus and loss consumption positive value for temperature degree 变化曲线图. from in can, low 于-50℃ low temperature 区, remove use 0.30份DCP and 4.00份HY-2045 increase to blending material, its increase rear blending material can modulus high increase blending material can modulus. this can can is due to 0.30份DCP and 4.00份HY-2045共同 increase 容HDPE/GTR blending material 时, formed stability interface 层[由(b)图 in blending material in -50~25℃区间 inner relatively wide GTR versus 玻璃化转变峰], and meanwhile, a small amount of DCP引发HDPE自 crosslinked, make its crystallization degree reduce, can modulus reduce;而 a small amount of HY-2045引发GTR crosslinked, can modulus rise high, most make blending material can modulus relatively other blending material low. according to 文献资 material [13, 14], polymer in 玻璃化转变 process in, can modulus and its crosslinked density positive related 关系, is crosslinked density large, can modulus 也就越 large. from 图5 in can, HDPE/GTR blending material in GTR橡胶 versus in low temperature 区发生 obvious 玻璃化转变, increase rear blending material can modulus HY-2045 content increase 而不断 increase large, can amount HY-2045引发 GTR crosslinked reaction, make its separation active property significantly reduce, 玻璃化转变 temperature degree toward high temperature 区移动, 当HY-2045 content is 20.00份时, its versus degree crosslinked generate grade 转变松弛峰甚至“消失”, 如(b)图 in 示. due to HY-2045 remove blending material interface chemical crosslinked formed stability interface outer, amount HY-2045引发橡胶 versus 发生严 heavy crosslinked function, 当DCP again add blending system rear, has very less separation DCP参 and interface chemical increase 容, its very large separation as used for HDPE, 引发HDPE发生自 crosslinked function, make its crystallization degree significantly reduce, in crystallization process in, high degree crosslinked GTR also effect/influence HDPE separation 子链排入晶区而 crystallization process, 以至于形 formed 不完善 晶区. therefore, HDPE/GTR blending material in temperature degree high 于40℃时, HDPE部 separation and 晶区边缘就迅 speed 发生松动转变, obvious α*转变峰;至于 more high temperature degree 区域 转变 is in 晶区“崩塌” process in, inner, 晶区边缘以 and 贯穿晶区 and non separation 子链 松弛转变, its easy Sample made process, hot history and rise temperature speed rate and other effect/influence [15].

        结论

         reaction type increase agent DCP and HY-2045 in improvement HDPE/GTR blending material versus property meanwhile, for blending material crystallization property can has effect/influence. increase agent add 入, make blending material crystallization degree significantly reduce, crystallization temperature degree and melt temperature degree basic upper maintain 不变, meanwhile blending material crystallization degree increase agent content increase 而不断 reduce. another, increase rear blending material, due to in interface 处发生 chemical crosslinked reaction and DCP for HDPE基体 versus crosslinked phenomenon, make blending material crystallization degree in reduce meanwhile crystallization defect significantly increase, make its in high temperature 区出现 comparison obvious 松弛转变.

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