CN108795018B - Preparation method of polyurethane/cellulose multifunctional shape memory polymer material - Google Patents
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 62
- 229920002678 cellulose Polymers 0.000 title claims abstract description 52
- 239000001913 cellulose Substances 0.000 title claims abstract description 52
- 229920000431 shape-memory polymer Polymers 0.000 title claims abstract description 29
- 239000002861 polymer material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 9
- 235000010980 cellulose Nutrition 0.000 claims abstract description 51
- 239000000243 solution Substances 0.000 claims abstract description 38
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 34
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 34
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 34
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
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- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明涉及一种聚氨酯/纤维素多功能形状记忆高分子材料的制备方法，将离子溶剂、无水乙醇和去离子水进行混合后采用超声分散得到澄清透明的复合溶液；向复合溶液中加入硅烷偶联剂，并滴加乙酸调节溶液PH，搅拌溶液使硅烷偶联剂发生水解反应；向溶液中加入微晶纤维素，充分搅拌后使用布氏漏斗进行过滤；步取滤渣，将滤渣置于冷冻干燥机进行冷冻干燥得到功能化的微晶纤维素；步骤5向聚氨酯和N‑甲基吡咯烷酮的混合溶液中加入功能化的微晶纤维素、罗丹明并搅拌。本发明将功能化后的纤维素和聚氨酯以及罗丹明进行溶液浇注制备复合材料，构筑基于纤维素基元的二元杂合网络，制备出具备高强度、高韧性的兼顾温度响应和紫外光响应的形状记忆高分子材料。
The invention relates to a method for preparing a polyurethane/cellulose multifunctional shape memory polymer material. After mixing an ionic solvent, anhydrous ethanol and deionized water, ultrasonic dispersion is used to obtain a clear and transparent composite solution; silane is added to the composite solution. The coupling agent was added dropwise with acetic acid to adjust the pH of the solution, and the solution was stirred to make the silane coupling agent hydrolyzed; microcrystalline cellulose was added to the solution, and after full stirring, a Buchner funnel was used for filtration; The freeze-drying machine performs freeze-drying to obtain functionalized microcrystalline cellulose; in step 5, functionalized microcrystalline cellulose and rhodamine are added to the mixed solution of polyurethane and N-methylpyrrolidone and stirred. In the present invention, the functionalized cellulose, polyurethane and rhodamine are solution-casted to prepare composite materials, a binary hybrid network based on cellulose primitives is constructed, and a high-strength and high-toughness composite material with both temperature response and ultraviolet light response is prepared. shape memory polymer materials.
Description
Technical Field
The invention relates to a preparation method of a shape memory polymer material, in particular to a preparation method of a polyurethane/cellulose multifunctional shape memory polymer material.
Background
Polymeric shape memory materials are a class of stimulus-responsive materials that rely on a change in shape. The stimuli that induce the shape memory effect may be temperature, current, magnetic field, pH, humidity, light, etc. The material has the characteristics of large deformation and large-range adjustable mechanical property, and has the advantages of low price, light weight and easy processing and forming. In recent years, shape memory polymers show great application prospects in the field of intelligent materials due to excellent properties of the shape memory polymers, such as intelligent sensors, intelligent textile materials, the slow release direction of biomedical drugs and great application in the field of aerospace. Polyurethanes (SMPU) are shape memory polymers with hard and soft segments, which have the advantage that the shape memory function can be adjusted or changed by controlling the ratio of the hard and soft segments or by introducing other groups. SMPU has excellent mechanical property and good biocompatibility, the designable range of the memory temperature is wide, the deformation quantity is large, the shape memory effect is good, the processability is good, but the defects of slow shape recovery speed, poor repeated memory effect, low mechanical strength, single response function and the like exist due to the phase separation of soft and hard sections, and the traditional shape memory polyurethane material can not meet the requirements of the traditional shape memory polyurethane material in some fields such as aerospace and the like. The problems of improving the mechanical strength, the shape recovery rate, preparing the multi-response functional material and the like so as to widen the application field of the material are always needed to be solved.
Cellulose is an inexhaustible renewable resource. The cellulose has excellent physicochemical properties of high modulus, large specific surface area and the like, and compared with synthetic polymers, the cellulose also has the advantages of complete degradation, no toxicity, no pollution, easy modification, good biocompatibility, renewability and the like, is considered as a main raw material of world energy and chemical industry in the future, and is expected to replace glass fiber and other synthetic fibers. At present, a plurality of scientific researchers strengthen the polyurethane material by using cellulose, and a series of remarkable results are obtained, and the strength and the modulus of the polyurethane material are greatly enhanced due to the rigid three-dimensional hydrogen bond network formed by the introduction of the cellulose. However, most of the materials have a greatly reduced toughness while using cellulose to toughen polyurethane, so that how to well maintain the shape memory function of the polyurethane under the condition of controlling the polyurethane phase separation degree and prepare a polyurethane material with both strength and toughness to meet the requirements in the fields of aerospace and intelligent sensors is very demanding.
Rhodamine is an ideal material which has excellent optical properties, low cost and good stability and is often used as a fluorescent material and a biological probe. The compound has a great application prospect in the aspects of biosensors and drug slow release, but the compound is hardly reported to be used as a fluorescent agent and a structural component of a high polymer material so as to regulate and control the physical and chemical properties of the material.
Disclosure of Invention
The invention aims to overcome the difficulty that the existing memory material can not realize a polyurethane material with high strength and high toughness, and provides a preparation method of a polyurethane/cellulose multifunctional shape memory polymer with high strength and high toughness. Compared with the traditional solvent reaction system, the grafting efficiency of the cellulose is greatly improved (2) the functionalized cellulose, polyurethane and rhodamine are subjected to solution casting to prepare the composite material, a binary heterozygosis network based on the cellulose elements is constructed, and the multifunctional shape memory polymer material which has high strength and high toughness and gives consideration to temperature response and ultraviolet response is prepared. Compared with pure polyurethane, the prepared composite functional material has the advantages that the tensile strength is increased by 200%, the elongation at break is increased by 300%, the composite functional material has a quick temperature response function and a quick photoresponse function, and the shape memory recovery rate reaches 92%.
The technical scheme adopted by the invention is as follows: a process for preparing the multifunctional shape-memory high-molecular polyurethane/cellulose material includes such steps as
step 5, adding functionalized microcrystalline cellulose into the mixed solution of polyurethane and N-methyl pyrrolidone and stirring;
step 6, adding rhodamine into the solution for reaction;
and 7, volatilizing the solvent in the reaction solution to obtain the dried polyurethane/cellulose multifunctional shape memory polymer material.
Further, the volume ratio of the absolute ethyl alcohol to the deionized water in the step 1 is 2-3 to 1.
Further, acetic acid was added dropwise in step 2 to adjust pH = 4-5.
Further, the hydrolysis reaction in step 2 was carried out at 80 ℃.
Furthermore, the mass ratio of the polyurethane to the N-methyl pyrrolidone in the mixed solution of the polyurethane and the N-methyl pyrrolidone is 1: 10.
Furthermore, the addition amount of the functionalized microcrystalline cellulose is 5-10% of the mass of the polyurethane
Furthermore, the adding amount of rhodamine is 5-20% of the weight of the functional cellulose
Further, the volatilization of the solvent in step 7 is performed at room temperature.
The beneficial effects produced by the invention comprise: the invention relates to a multifunctional shape memory polymer material prepared by performing homogeneous functionalization reaction on microcrystalline cellulose to regulate and control grafting efficiency, and forming a cellulose-based dual-reinforcement and toughening network by utilizing the functionalized cellulose and adding rhodamine and polyurethane, which is particularly shown in the specification
(1) The invention discloses a silanized grafting solvent system of green clean microcrystalline cellulose, which can perform homogenization reaction under the condition of dissolving cellulose due to the existence of an ionic solvent. Compared with the traditional system of ethanol and water, the environment-friendly solvent can be recovered, the pollution to the environment can be reduced, the requirement of green sustainable development is met, and the grafting efficiency is greatly improved.
(2) Compared with a pure polyurethane material, the shape memory polymer material prepared from the microcrystalline cellulose functionalized by silane and polyurethane and rhodamine has the characteristics of high strength and high toughness, the strength of the shape memory polymer material is increased by 200% compared with that of the pure polyurethane material, and the elongation at break of the shape memory polymer material is increased by 300%. The contradiction of mutual exclusion of the strength and the toughness of the material is solved, so that the material can be coordinated and exist together. And the intelligent material with dual stimulation responses of temperature and ultraviolet light is prepared, the shape memory function controlled by the temperature is greatly improved, and the shape recovery rate is as high as 92%. The material can be applied to the fields of temperature sensors with large strain and aerospace.
(3) The invention greatly widens the application range of the cellulose, and takes the cellulose as an element to form a dual network structure by controlling the silanization degree shown by the cellulose, so that the cellulose can play dual roles of a reinforcing agent and a chemical cross-linking agent, an important function of the cellulose is developed, and a new application direction is opened up for the cellulose which is industrially produced later.
Drawings
FIG. 1 is a graph showing the UV response function and curves of a polyurethane/cellulose composite;
fig. 2 is a scanning electron microscope image of a tensile fracture surface of the polyurethane/cellulose composite material.
Detailed Description
The present invention is explained in further detail below with reference to the drawings and the detailed description, but it should be understood that the scope of the present invention is not limited by the detailed description.
Example 1
(1) Homogeneous functionalization reaction of microcrystalline cellulose
Firstly, preparing a green novel composite solvent: accurately weighing 19g of 1-allyl, 3-methylimidazolium chloride ionic solvent, weighing 10ml of absolute ethyl alcohol and 5ml of deionized water, adding the absolute ethyl alcohol and the 5ml of deionized water into a three-neck flask, and performing ultrasonic dispersion for 10min to obtain a clear and transparent composite solution. 1g of silane coupling agent is added, acetic acid is added dropwise to adjust the pH =4, and then the mixture is magnetically stirred for 1 hour at 80 ℃ to cause the silane coupling agent to generate hydrolysis reaction. And weighing 1g of microcrystalline cellulose, adding the microcrystalline cellulose into a three-neck flask, continuously stirring for reacting for 3 hours, cooling to room temperature, filtering and washing by using a Buchner funnel to obtain filter residues, and washing for multiple times to remove the incompletely reacted silane coupling agent. And finally, carrying out freeze drying on the reacted microcrystalline cellulose for 48h by using a freeze dryer to obtain the functionalized microcrystalline cellulose.
(2) Preparation of high-strength high-toughness polyurethane/cellulose multifunctional shape memory polymer material
Dissolving 2g of dried polyurethane in 20g N-methylpyrrolidone solution, magnetically stirring at room temperature for 6h to obtain clear and transparent dissolved solution, adding 0.1g of functionalized microcrystalline cellulose, continuing to stir for 12h, finally adding 5mg of rhodamine, dispersing for 30min by using an ultrasonic dispersion machine, continuing to stir at room temperature for 10h to prepare a flat and regular membrane material, pouring the reacted solution into an evaporation dish of polytetrafluoroethylene, and volatilizing the solvent at room temperature for 1 week to obtain the dried polyurethane/cellulose multifunctional shape memory polymer material
Example 2
(1) Homogeneous functionalization reaction of microcrystalline cellulose
The functionalization reaction of microcrystalline cellulose is carried out according to example 1, 19g of 1-allyl, 3-methylimidazolium chloride ionic solvent is accurately weighed, 12.5ml of absolute ethyl alcohol and 5ml of deionized water are weighed and added into a three-neck flask, and a clear and transparent composite solution is obtained after 10min of ultrasonic dispersion. 1g of silane coupling agent was added, acetic acid was added dropwise to adjust pH =4.5, and the mixture was magnetically stirred at 80 ℃ for 1 hour to cause hydrolysis reaction of the silane coupling agent. And weighing 1g of microcrystalline cellulose, adding the microcrystalline cellulose into a three-neck flask, continuously stirring for reacting for 3 hours, cooling to room temperature, filtering and washing by using a Buchner funnel to obtain filter residues, and washing for multiple times to remove the incompletely reacted silane coupling agent. And finally, carrying out freeze drying on the reacted microcrystalline cellulose for 48h by using a freeze dryer to obtain the functionalized microcrystalline cellulose.
(2) Preparation of high-strength high-toughness polyurethane/cellulose multifunctional shape memory polymer material
Dissolving 2g of dried polyurethane in a 20g N-methyl pyrrolidone solution, magnetically stirring at room temperature for 6h to obtain a clear and transparent solution, adding 0.15g of functionalized microcrystalline cellulose, continuing to stir for 12h, finally adding 18.75mg of rhodamine, dispersing for 30min by using an ultrasonic dispersion machine, continuing to stir at room temperature for 10h, pouring the reacted solution into a polytetrafluoroethylene evaporation dish, and volatilizing the solvent at room temperature for 1 week to obtain the dried polyurethane/cellulose multifunctional shape memory polymer material.
Example 3
(1) Homogeneous functionalization reaction of microcrystalline cellulose
The functionalization reaction of microcrystalline cellulose is carried out according to example 1, 19g of 1-allyl, 3-methylimidazolium chloride ionic solvent is accurately weighed, 15ml of absolute ethyl alcohol and 5ml of deionized water are weighed and added into a three-neck flask, and a clear and transparent composite solution is obtained after 10min of ultrasonic dispersion. 1g of silane coupling agent is added, acetic acid is added dropwise to adjust the pH =5, and then the mixture is magnetically stirred at 80 ℃ for 1 hour to cause the silane coupling agent to generate hydrolysis reaction. And weighing 1g of microcrystalline cellulose, adding the microcrystalline cellulose into a three-neck flask, continuously stirring for reacting for 3 hours, cooling to room temperature, filtering and washing by using a Buchner funnel to obtain filter residues, and washing for multiple times to remove the incompletely reacted silane coupling agent. Finally, freeze-drying the reacted microcrystalline cellulose for 48 hours by using a freeze dryer to obtain the functionalized microcrystalline cellulose
(2) Preparation of high-strength high-toughness polyurethane/cellulose multifunctional shape memory polymer material
Dissolving 2g of dried polyurethane in a 20g N-methyl pyrrolidone solution, magnetically stirring at room temperature for 6h to obtain a clear and transparent solution, adding 0.2g of functionalized microcrystalline cellulose, continuing to stir for 12h, finally adding 40mg of rhodamine, dispersing for 30min by using an ultrasonic dispersion machine, continuing to stir at room temperature for 10h, pouring the reacted solution into a polytetrafluoroethylene evaporation dish, and volatilizing the solvent at room temperature for 1 week to obtain the dried polyurethane/cellulose multifunctional shape memory polymer material.
The tensile properties of the polyurethane/cellulose composite material prepared in the above example are shown in table 1, and the tensile strength and the elongation at break of the obtained polyurethane/cellulose composite material are both greatly improved compared with those of the memory polymer material prepared from the traditional polyurethane.
TABLE 1 tensile Properties of polyurethane/cellulose composites
| Sample (I) | Tensile Strength (MPa) | Modulus of elasticity (MPa) | Elongation at Break (%) |
| Pure polyurethane (comparison sample) | 3.0±0.2 | 25.9±2.6 | 267.3±26.2 |
| Example 1 | 5.4±0.1 | 19.6±2.1 | 686.1±9.3 |
| Example 2 | 5.1±0.1 | 19.7±1.3 | 713.2±34.3 |
| Example 3 | 5.8±0.3 | 19.1±1.3 | 706.5±22.9 |
FIG. 1 is a graph showing the UV response function and curves of a polyurethane/cellulose composite; as can be seen from FIG. 1, the prepared polyurethane/cellulose has excellent ultraviolet response function, the material is colorless and transparent when dissolved and dispersed in an N-methylpyrrolidone solution, and then the solution is changed from transparent to pink after being placed under 365nm ultraviolet light for 30min, and an absorption peak around 530nm appears in an ultraviolet absorption spectrum. As can be seen from the figure, the intensity of the absorption peak increases significantly with the increase of the irradiation time. The color of the solution changed from pink to colorless and transparent again after heating the solution at 80 ℃ for 10 min. The solution can be subjected to multiple cycles of ultraviolet irradiation-heating to cause the color to be changed from colorless and transparent to pink.
Fig. 2 is a scanning electron microscope image of a tensile fracture surface of the polyurethane/cellulose composite material. As can be seen, FIG. 2a is a tensile failure plane of a pure polyurethane material, in which an irregular circular cell structure interconnected by small pores is clearly observed, and which is a loose, fluffy surface. The polyurethane/cellulose composite material is broken to form a three-dimensional cross-linked three-dimensional network structure, and can be bonded with a tight interface formed between the cellulose and the matrix polyurethane, as shown in fig. 2 b.
The invention constructs double functions of cellulose as a cross-linking agent and a reinforcement of a double-network framework, the introduced rhodamine B not only serves as a switch of a photosensitizer, but also is a novel functional material with a structure element distribution that a high-molecular toughening agent creates a double-network structure, the material is endowed with high toughness and high recovery rate and efficient thermal and optical multiple response, the contradiction that the material is difficult to coexist in the material, the material has high strength and high toughness and the recovery rate of the shape memory composite material is effectively improved, and on the other hand, the material has multiple response functions. The defect of the original shape memory function is overcome, the physical and chemical properties of the sensor are greatly improved, the application field of the sensor is greatly expanded, an optimized solution idea is particularly provided on the design of a large strain sensor, and the sensor also conforms to the concept of the modern green bio-based sustainable development.
The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the content of the embodiment. It will be apparent to those skilled in the art that various changes and modifications can be made within the technical scope of the present invention, and any changes and modifications made are within the protective scope of the present invention.
Claims (6)
1. A preparation method of a polyurethane/cellulose multifunctional shape memory polymer material is characterized by comprising the following steps: comprises the following steps
Step 1, mixing an ionic solvent, absolute ethyl alcohol and deionized water, and then performing ultrasonic dispersion to obtain a clear and transparent composite solution;
step 2, adding a silane coupling agent into the composite solution, dropwise adding acetic acid to adjust the pH value of the solution, and stirring the solution to enable the silane coupling agent to generate a hydrolysis reaction;
step 3, adding microcrystalline cellulose into the solution, fully stirring, and filtering by using a Buchner funnel;
step 4, taking filter residue, and placing the filter residue in a freeze dryer for freeze drying to obtain functionalized microcrystalline cellulose;
step 5, adding functionalized microcrystalline cellulose into the mixed solution of polyurethane and N-methyl pyrrolidone and stirring;
step 6, adding rhodamine into the solution for reaction;
step 7, volatilizing the solvent in the reaction solution to obtain a dry polyurethane/cellulose multifunctional shape memory polymer material;
the addition amount of the functionalized microcrystalline cellulose is 5-10% of the mass of the polyurethane;
the addition amount of rhodamine is 5-20% of the mass of the functional cellulose.
2. The method for preparing a polyurethane/cellulose multifunctional shape memory polymer material according to claim 1, wherein the method comprises the following steps: in the step 1, the volume ratio of the absolute ethyl alcohol to the deionized water is 2 to 1.
3. The method for preparing a polyurethane/cellulose multifunctional shape memory polymer material according to claim 1, wherein the method comprises the following steps: in step 2, acetic acid was added dropwise to adjust pH = 5.
4. The method for preparing a polyurethane/cellulose multifunctional shape memory polymer material according to claim 1, wherein the method comprises the following steps: the hydrolysis reaction in step 2 was carried out at 80 ℃.
5. The method for preparing a polyurethane/cellulose multifunctional shape memory polymer material according to claim 1, wherein the method comprises the following steps: the mass ratio of the polyurethane to the N-methyl pyrrolidone in the mixed solution of the polyurethane and the N-methyl pyrrolidone is 1: 10.
6. The method for preparing a polyurethane/cellulose multifunctional shape memory polymer material according to claim 1, wherein the method comprises the following steps: the evaporation of the solvent in step 7 is carried out at room temperature.
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| CN110204883B (en) * | 2019-05-22 | 2021-03-26 | 南京林业大学 | Preparation method of polyurethane cellulose composite oil-water separation thermal insulation aerogel |
| CN112898636B (en) * | 2021-02-18 | 2022-02-18 | 陕西科技大学 | A kind of preparation method of self-healing cellulose-based plastic |
| CN113061274B (en) * | 2021-03-17 | 2022-11-22 | 广东工业大学 | Multi-structure color-changing intelligent optical film driven by multi-shape memory and preparation method and application thereof |
| CN115785531B (en) * | 2022-09-20 | 2023-11-03 | 南京林业大学 | Functionalized microcrystalline cellulose-based double-network gel film and preparation method thereof |
| CN116284968A (en) * | 2023-03-24 | 2023-06-23 | 四川大学华西医院 | Solvent-free preparation of shape memory polyurethane/biomass fiber composite foam and method for regulating and controlling plantar pressure of shape memory polyurethane/biomass fiber composite foam |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004145A (en) * | 2014-05-12 | 2014-08-27 | 华南理工大学 | Method for preparation of bagasse-grafted methyl methacrylate copolymer by solid-phase method |
| CN104292412A (en) * | 2014-10-10 | 2015-01-21 | 北京铁科首钢轨道技术股份有限公司 | Cellulose base polyurethane prepolymer as well as sealing material using cellulose base polyurethane prepolymer, preparation method and application of cellulose base polyurethane prepolymer |
| CN104558421A (en) * | 2014-10-10 | 2015-04-29 | 河北科技大学 | Preparation method of grafted cellulose medicinal molecule with pH/temperature responsiveness |
| CN105504235A (en) * | 2014-09-26 | 2016-04-20 | 中国科学院大连化学物理研究所 | Method for producing cellulose-grafted polylactic acid copolymer from cellulose |
| CN107501898A (en) * | 2017-07-05 | 2017-12-22 | 广东工业大学 | A kind of conductivity type shape memory macromolecule composite material with heterogeneous biswitch and its preparation method and application |
-
2018
- 2018-06-22 CN CN201810649692.0A patent/CN108795018B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004145A (en) * | 2014-05-12 | 2014-08-27 | 华南理工大学 | Method for preparation of bagasse-grafted methyl methacrylate copolymer by solid-phase method |
| CN105504235A (en) * | 2014-09-26 | 2016-04-20 | 中国科学院大连化学物理研究所 | Method for producing cellulose-grafted polylactic acid copolymer from cellulose |
| CN104292412A (en) * | 2014-10-10 | 2015-01-21 | 北京铁科首钢轨道技术股份有限公司 | Cellulose base polyurethane prepolymer as well as sealing material using cellulose base polyurethane prepolymer, preparation method and application of cellulose base polyurethane prepolymer |
| CN104558421A (en) * | 2014-10-10 | 2015-04-29 | 河北科技大学 | Preparation method of grafted cellulose medicinal molecule with pH/temperature responsiveness |
| CN107501898A (en) * | 2017-07-05 | 2017-12-22 | 广东工业大学 | A kind of conductivity type shape memory macromolecule composite material with heterogeneous biswitch and its preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| "Dissolution of fir powder and its graft copolymer in ionic liquid";Liying Guo等;《Eur. J. Wood Prod》;20100504;第383-389页 * |
| "Dissolution of micracryatalline cellulose and its graft copolymer in ionic liquid of 1-allyl-3-ethylimidazolium chloride";Liying Guo等，;《e-Polymer》;20091021;第1-11页 * |
| "制浆造纸及纤维素工业离子液体的应用";张应中;《技术与市场》;20130715;第20卷(第7期);第85-86页 * |
| "微晶纤维素/聚氨酯形状记忆复合材料的制备";蔡晨阳等，;《第三届中国国际复合材料科技大会论文集》;20171021;第285-290页 * |
| "甘蔗渣纤维素的改性及应用进展";劳超等，;《广州化学》;20170430;第42卷(第2期);第71-76页 * |
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