CN106589266A - Lightweight grafting composite elastic material and preparation method thereof - Google Patents

Abstract

The invention discloses a lightweight grafting composite elastic material, prepared from the following raw materials in parts by weight: 3-4 parts of 4-dimethylamino-pyridine, 1-2 parts of triethylamine, 0.1-0.3 part of 2-bromoisobutyryl bromide, 2-4 parts of potassium zirconium carbonate, 0.6-1 part of pyromellitic acid dianhydride, 0.4-1 part of trimethylolpropane, 2-4 parts of abietyl alcohol, 1-2 parts of nickel aminosulfonate, 1-2 parts of 1-allyl-3-methylimidazolium chloride, 50-60 parts of methyl methacrylate, 10-13 parts of carbon nanotube, 40-51 parts of n-butyl acrylate, 0.7-1 part of copper bromide, 1.6-2 parts of pentamethyl diethylene triamine, 1-2 parts of copper powder, 3-5 parts of trimellitate, 0.1-0.2 part of alkanolamide, 3-4 parts of light calcium carbonate, and an appropriate amount of glycol, dimethylfomamide, chloroform, thionyl chloride and 95-98% nitric acid. The lightweight grafting composite elastic material disclosed by the invention is light in weight, is convenient for transportation and installation, is convenient to use, and is superior in comprehensive performance.

Description

A kind of lightweight grafting composite elastic material and preparation method thereof

Technical field

The present invention relates to elastomeric material technical field, more particularly to a kind of lightweight grafting composite elastic material and its preparation side Method.

Background technology

Thermoplastic elastomer (TPE) is a kind of special macromolecular material, both with elasticity, and with plasticity, can extensively be applied In the key areas of the national economy such as packaging material, auto parts, binding agent, clothing, biomedicine.Thermoplastic elastomer (TPE) has one Individual common the characteristics of, i.e., be nearly all phase-separated system, and at room temperature one is mutually rubber phase, and another phase is hard phase.Vitrification The very low rubber of transition temperature is used as matrix, and the higher hard phase of glass transition temperature is then dispersed in rubber as dispersion phase Play a part of physical crosslinking point in matrix.For thermoplastic elastomer (TPE), mutually make elastomer that there is intensity firmly, and rubber mutually makes Elastomer has ductility, and by control ratio between the two the elastomer of different mechanical properties can be obtained.But, with biography System vulcanite is compared, and thermoplastic elastomer (TPE) also has disadvantages that, this kind of elastomer is susceptible to permanent compression set, its shape Stability, thermostability and solvent resistance are also bad.Therefore, in order to obtain the thermoplastic elastic material of superior performance, need Controllable optimization design is carried out to the chain structure of thermoplastic elastomer (TPE) so as to hard mutually to bring out the best in each other with rubber, preferably played each From effect；

CNT possesses excellent mechanical property and electric property, and heat stability is high, and with larger draw ratio, and density is very It is low, so be considered as to prepare the preferable Nano filling of high performance material even so, because the dispersibility of CNT is very poor, Easily aggregation is reunited in polymeric matrix, is had a great impact to the performance of composite, therefore greatly limit carbon The large-scale application of nanotube, in order to improve the degree of scatter of CNT, can be with Bian things when composite is prepared Reason or the method for chemistry are processed, such as using surfactant, dissolve blending, solution blending, surface is modified, be co-precipitated, surpass The method such as sound dispersion and in-situ polymerization, CNT is made into Nano filling introducing elastic matrix increases can its modulus, and this is The hydrodynamics effect and the interaction between polymer and filler caused after due to adding CNT increased bullet What the crosslink density of gonosome was caused.Generally, introduce Nano filling after, elastic composite occur Payne effects and Mullins effects, the elastic composite based on CNT is no exception.It should be noted that Payne effects are referred to The storage moduluss of elastic composite decline to a great extent as strain amplitude increase occurs, typical non-linear behavior occur, At present being that the network being made up of filler in material is gradually destroyed as strain increases most reasonably is explained to this phenomenon, this Individual network is not only formed by the interaction between filler and filler, also including between polymer and filler and polymer Interact.It is exactly Mullins effects to occur delayed strain softening phenomenon when elastic composite carries out second stretching Should, this hysteresis are due to introducing the Nano filling that cannot be deformed upon, material is generated in drawing process Energy dissipation, destroys a part and the polymer molecular chain of contribution function is played to elastomeric network and is caused.For such Composite, crystallization can be formed due to molecular chain orientation and plays a part of similar physical crosslinking points when stretching at room temperature, this The molten point of a little crystallizations is about 48 DEG C, therefore its strain can not be replied at once after the stress for applying is removed.When temperature is raised sample After the crystal training formed in product is melted, the conformation of polymer molecular chain is just gradually recovered under the driving of entropic elasticity.Due to carbon nanometer Pipe can absorb near infrared light, it is also possible to which heat is produced in the presence of electric current raises the temperature of sample, promotes as physics The crystallization of crosslinking points is dissolved, here it is there is the origin of shape memory.There is many being similar to prepare using CNT again later The report of the thermoplastic elastomer composite material of shape memory function；

Inorganic nano-filler introducing polymeric matrix can be made into the material in mechanical property, electric conductivity, heat stability and breathed freely The aspects such as property increase significantly and improve.For such nano composite material, their macro property and Nano filling Distance between size, interfacial interaction and filler is closely related.CNT is introduced by bullet by the method for physical blending The research of gonosome has a lot, however, for the research that glycerol polymerization prepares elastomer is carried out as initiation point using CNT Also rarely have and be related to, carrying out one kettle way glycerol polymerization by the method for chemistry can effectively increase phase between Nano filling and matrix Interaction so as in being better dispersed in matrix, significantly increases its interface interaction power, so as to further improve its performance, therefore Prepare this kind of high-performance thermoplastic elastomer and there is important practical significance.

The content of the invention

The object of the invention is exactly to make up the defect of prior art, there is provided a kind of lightweight grafting composite elastic material and its Preparation method.

The present invention is achieved by the following technical solutions：

A kind of lightweight is grafted composite elastic material, and it is by made by the raw material of following weight parts：

DMAP 3-4, triethylamine 1-2,2- bromine isobutyl acylbromide 0.1-0.3, potassium zirconium carbonate 2-4, pyromellitic acid dianhydride 0.6-1, trimethylolpropane 0.4-1, abienol 2-4, nickel sulfamic acid 1-2, chlorination 1- pi-allyl -3- Methylimidazole. 1-2, first Base acrylic acid methyl ester. 50-60, CNT 10-13, n-butyl acrylate 40-51, copper bromide 0.7-1, pentamethyl divinyl three Amine 1.6-2, copper powder 1-2, trimellitate 3-5, alkanolamide 0.1-0.2, precipitated calcium carbonate 3-4, ethylene glycol, dimethyl formyl Amine, chloroform, thionyl chloride, 95-98% nitric acid it is appropriate.

A kind of described lightweight is grafted the preparation method of composite elastic material, comprises the following steps：

（1）Above-mentioned potassium zirconium carbonate is added in the deionized water of its weight 37-40 times, is stirred, Deca 3-5mol/l Hydrochloric acid, regulation pH is 1-2, and the slow high-temperature that rises is 60-70 DEG C, the above-mentioned alkanolamide of addition, insulated and stirred 10-20 minute, plus Enter above-mentioned CNT, stir to room temperature, filter, by precipitation washing 3-4 time, normal temperature drying obtains composite carbon nanometer tube；

（2）Above-mentioned composite carbon nanometer tube is added in its weight 100-130 times, 95-98% nitric acid, 140-150 is sent to DEG C oil bath in, insulated and stirred 10-12 hour, sucking filtration washes precipitate with deionized water 2-3 time, at 54-60 DEG C be vacuum dried 1-2 hours, obtain acidifying CNT；

（3）Above-mentioned nickel sulfamic acid, pyromellitic acid dianhydride are mixed, in being added to the ethylene glycol of compound weight 70-80 times, is stirred Mix uniform, obtain alcohol dispersion liquid；

（4）Above-mentioned acidifying CNT is added in the thionyl chloride of its weight 20-30 times, the insulated and stirred at 60-70 DEG C 20-25 hours, are distilled off thionyl chloride, in being added to above-mentioned alcohol dispersion liquid, in being sent to 110-120 DEG C of oil bath, and insulation 46-50 hours, sucking filtration washes precipitation dimethylformamide 2-3 time, and 1-2 hours are vacuum dried at 40-50 DEG C, obtains hydroxyl Carbon nano tube；

（5）Above-mentioned hydroxyl carbon nano tube, precipitated calcium carbonate are mixed, in being added to the chloroform of compound weight 17-20 times, plus Enter above-mentioned DMAP, triethylamine, in being sent to ice-water bath, the above-mentioned 2- bromine isobutyl acylbromides of Deca, stirring reaction 3-4 is little When, discharging is incubated at room temperature reaction 46-50 hours, and sucking filtration washs filter cake chloroform, deionized water 2-3 time successively, 1-2 hours are vacuum dried at 40-50 DEG C, initiator is obtained carbon nano-tube modified；

（6）By above-mentioned abienol at 80-90 DEG C insulated and stirred 3-5 minute, add above-mentioned trimethylolpropane, insulated and stirred 10-20 minutes, add above-mentioned initiator carbon nano-tube modified, ultrasonic 10-15 minutes, obtain alkyl modified CNT；

（7）By above-mentioned methyl methacrylate, n-butyl acrylate, alkyl modified CNT, pentamethyl-diethylenetriamine, bromine Change copper mixing, in being added to the dimethylformamide of compound weight 10-16 times, add above-mentioned copper powder, be passed through nitrogen, freezing is dry Dry 20-30 minutes, in being sent to 65-70 DEG C of oil bath, insulated and stirred 1-2 hour adds above-mentioned tetrahydrofuran, stirs, In adding the methanol of mixed system weight 2-3 times, remaining each raw material is added, stirred, stand 2-3 hours, sucking filtration will be precipitated Washed 3-4 time successively with dimethylformamide, deionized water, 10-12 hours are vacuum dried at 40-50 DEG C, obtain described compound Elastomeric material.

It is an advantage of the invention that：The present invention is to carry out acidification to CNT in concentrated nitric acid first, then by shape Into carboxyl carry out chloride with thionyl chloride, then there is acylation reaction with ethylene glycol, so as to introduce in carbon nano tube surface Hydroxyl, most relief hydroxyl react with 2- bromine isobutyl acylbromides, thus initiation point can be modified in carbon nano tube surface, carry out Controllable glycerol polymerization, finally on carbon Nanosurface graft acrylic acid N-butyl and methyl methacrylate copolymer；Carbon Nanotube is connected with the graft polymers as matrix by chemical bond, therefore has stronger interfacial interaction, can be with In being effectively dispersed in polymer, reunion will not be formed, and introduce CNT as polynary physical crosslinking point, when answering masterpiece When on these thermoplastic elastomer composite materials, scattered CNT is hooked as physical crosslinking due to there are these Point, stress can be shifted successfully, and so as to avoid stress concentration occurs to early Materials Fracture, therefore the tensile property of finished product are obtained Very big lifting is arrived, while CNT can significantly increase the mechanical property of material as rigid physical crosslinking point；

The material light weight of the present invention, is readily transported and installs, and easy to use, combination property is superior.

Specific embodiment

A kind of lightweight is grafted composite elastic material, and it is by made by the raw material of following weight parts：

DMAP 3, triethylamine 1,2- bromine isobutyl acylbromides 0.1, potassium zirconium carbonate 2, pyromellitic acid dianhydride 0.6, three hydroxyl first Base propane 0.4, abienol 2, nickel sulfamic acid 1, the allyl methyl imidazoles 1 of chlorination 1, methyl methacrylate 50, CNT 10th, n-butyl acrylate 40, copper bromide 0.7, pentamethyl-diethylenetriamine 1.6, copper powder 1, trimellitate 3, alkanolamide 0.1st, precipitated calcium carbonate 3, ethylene glycol, dimethylformamide, chloroform, thionyl chloride, 95% nitric acid are appropriate.

A kind of described lightweight is grafted the preparation method of composite elastic material, comprises the following steps：

（1）Above-mentioned potassium zirconium carbonate is added in the deionized water of 37 times of its weight, is stirred, the hydrochloric acid of Deca 3mol/l, It is 1 to adjust pH, and the slow high-temperature that rises is 60 DEG C, adds above-mentioned alkanolamide, insulated and stirred 10 minutes to add above-mentioned carbon nanometer Pipe, stirs to room temperature, filters, and by precipitation washing 3 times, normal temperature drying obtains composite carbon nanometer tube；

（2）Above-mentioned composite carbon nanometer tube is added in 100 times of its weight, 95% nitric acid, in being sent to 140 DEG C of oil bath, Insulated and stirred 10 hours, sucking filtration washes precipitate with deionized water 2 times, is vacuum dried 1 hour at 54 DEG C, must be acidified carbon nanometer Pipe；

（3）Above-mentioned nickel sulfamic acid, pyromellitic acid dianhydride are mixed, in being added to the ethylene glycol of 70 times of compound weight, stirring Uniformly, alcohol dispersion liquid is obtained；

（4）Above-mentioned acidifying CNT is added in the thionyl chloride of 20 times of its weight, insulated and stirred 20 hours at 60 DEG C, Thionyl chloride is distilled off, in being added to above-mentioned alcohol dispersion liquid, in being sent to 110 DEG C of oil bath, 46 hours is incubated, sucking filtration will Precipitation dimethylformamide is washed 2 times, is vacuum dried 1 hour at 40 DEG C, obtains hydroxyl carbon nano tube；

（5）Above-mentioned hydroxyl carbon nano tube, precipitated calcium carbonate are mixed, in being added to the chloroform of 17 times of compound weight, is added Above-mentioned 4 dimethylamino naphthyridine, triethylamine, in being sent to ice-water bath, above-mentioned 2 bromine isobutyl acylbromide of Deca, stirring reaction 3 hours goes out Material, is incubated at room temperature reaction 46 hours, and sucking filtration successively washs filter cake chloroform, deionized water 2 times, the vacuum at 40 DEG C It is dried 1 hour, obtains initiator carbon nano-tube modified；

（6）By above-mentioned abienol at 80 DEG C insulated and stirred 3 minutes, add above-mentioned trimethylolpropane, insulated and stirred 10 minutes, Add above-mentioned initiator carbon nano-tube modified, ultrasound 10 minutes obtains alkyl modified CNT；

（7）By above-mentioned methyl methacrylate, n-butyl acrylate, alkyl modified CNT, pentamethyl-diethylenetriamine, bromine Change copper mixing, in being added to the dimethylformamide of 10 times of compound weight, add above-mentioned copper powder, be passed through nitrogen, lyophilization 20 minutes, in being sent to 65 DEG C of oil bath, insulated and stirred 1 hour added above-mentioned tetrahydrofuran, stirs, and adds mixture Be 2 times of weight methanol in, add remaining each raw material, stir, stand 2 hours, sucking filtration, by precipitation dimethyl formyl Amine, deionized water are washed successively 3 times, are vacuum dried 10 hours at 40 DEG C, obtain the composite elastic material.

Performance test：

Elongation at break：518%；

Tensile strength：7.3N/mm²。

Claims (2)

1. a kind of lightweight is grafted composite elastic material, it is characterised in that it is by made by the raw material of following weight parts：

DMAP 3-4, triethylamine 1-2,2- bromine isobutyl acylbromide 0.1-0.3, potassium zirconium carbonate 2-4, pyromellitic acid dianhydride 0.6-1, trimethylolpropane 0.4-1, abienol 2-4, nickel sulfamic acid 1-2, chlorination 1- pi-allyl -3- Methylimidazole. 1-2, first Base acrylic acid methyl ester. 50-60, CNT 10-13, n-butyl acrylate 40-51, copper bromide 0.7-1, pentamethyl divinyl three Amine 1.6-2, copper powder 1-2, trimellitate 3-5, alkanolamide 0.1-0.2, precipitated calcium carbonate 3-4, ethylene glycol, dimethyl formyl Amine, chloroform, thionyl chloride, 95-98% nitric acid it is appropriate.

2. a kind of lightweight as claimed in claim 1 is grafted the preparation method of composite elastic material, it is characterised in that including following Step：

（1）Above-mentioned potassium zirconium carbonate is added in the deionized water of its weight 37-40 times, is stirred, Deca 3-5mol/l Hydrochloric acid, regulation pH is 1-2, and the slow high-temperature that rises is 60-70 DEG C, the above-mentioned alkanolamide of addition, insulated and stirred 10-20 minute, plus Enter above-mentioned CNT, stir to room temperature, filter, by precipitation washing 3-4 time, normal temperature drying obtains composite carbon nanometer tube；

（2）Above-mentioned composite carbon nanometer tube is added in its weight 100-130 times, 95-98% nitric acid, 140-150 is sent to DEG C oil bath in, insulated and stirred 10-12 hour, sucking filtration washes precipitate with deionized water 2-3 time, at 54-60 DEG C be vacuum dried 1-2 hours, obtain acidifying CNT；

（3）Above-mentioned nickel sulfamic acid, pyromellitic acid dianhydride are mixed, in being added to the ethylene glycol of compound weight 70-80 times, is stirred Mix uniform, obtain alcohol dispersion liquid；

（4）Above-mentioned acidifying CNT is added in the thionyl chloride of its weight 20-30 times, the insulated and stirred at 60-70 DEG C 20-25 hours, are distilled off thionyl chloride, in being added to above-mentioned alcohol dispersion liquid, in being sent to 110-120 DEG C of oil bath, and insulation 46-50 hours, sucking filtration washes precipitation dimethylformamide 2-3 time, and 1-2 hours are vacuum dried at 40-50 DEG C, obtains hydroxyl Carbon nano tube；

（5）Above-mentioned hydroxyl carbon nano tube, precipitated calcium carbonate are mixed, in being added to the chloroform of compound weight 17-20 times, plus Enter above-mentioned DMAP, triethylamine, in being sent to ice-water bath, the above-mentioned 2- bromine isobutyl acylbromides of Deca, stirring reaction 3-4 is little When, discharging is incubated at room temperature reaction 46-50 hours, and sucking filtration washs filter cake chloroform, deionized water 2-3 time successively, 1-2 hours are vacuum dried at 40-50 DEG C, initiator is obtained carbon nano-tube modified；

（6）By above-mentioned abienol at 80-90 DEG C insulated and stirred 3-5 minute, add above-mentioned trimethylolpropane, insulated and stirred 10-20 minutes, add above-mentioned initiator carbon nano-tube modified, ultrasonic 10-15 minutes, obtain alkyl modified CNT；

（7）By above-mentioned methyl methacrylate, n-butyl acrylate, alkyl modified CNT, pentamethyl-diethylenetriamine, bromine Change copper mixing, in being added to the dimethylformamide of compound weight 10-16 times, add above-mentioned copper powder, be passed through nitrogen, freezing is dry Dry 20-30 minutes, in being sent to 65-70 DEG C of oil bath, insulated and stirred 1-2 hour adds above-mentioned tetrahydrofuran, stirs, In adding the methanol of mixed system weight 2-3 times, remaining each raw material is added, stirred, stand 2-3 hours, sucking filtration will be precipitated Washed 3-4 time successively with dimethylformamide, deionized water, 10-12 hours are vacuum dried at 40-50 DEG C, obtain described compound Elastomeric material.