CN110684288B - Preparation method and application of special aid for improving polybutene-1 crystal form conversion rate - Google Patents
Preparation method and application of special aid for improving polybutene-1 crystal form conversion rate Download PDFInfo
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- CN110684288B CN110684288B CN201911092720.4A CN201911092720A CN110684288B CN 110684288 B CN110684288 B CN 110684288B CN 201911092720 A CN201911092720 A CN 201911092720A CN 110684288 B CN110684288 B CN 110684288B
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- 229920001748 polybutylene Polymers 0.000 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 37
- 239000013078 crystal Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- IHWUGQBRUYYZNM-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-3,4-dicarboxylic acid Chemical compound C1CC2(C(O)=O)C(C(=O)O)=CC1C2 IHWUGQBRUYYZNM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000344 soap Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 239000012265 solid product Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 5
- 229920002749 Bacterial cellulose Polymers 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005016 bacterial cellulose Substances 0.000 claims description 3
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 2
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 3
- 230000000996 additive effect Effects 0.000 claims 3
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000010128 melt processing Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 235000010980 cellulose Nutrition 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
- 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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
本发明涉及一种用于提高聚丁烯‑1晶型转化速率的专用助剂的制备方法及专用助剂的应用，属于高分子材料技术领域，具体包括将降冰片烯二羧酸皂金属盐白色固体粉末溶于N，N‑二甲基甲酰胺中并完全溶解；再缓慢滴加盐酸溶液，调节PH值至2‑5之间；将纤维素粉末加入到上述体系中，搅拌使其分散均匀；然后再加入滴加氢氧化钠溶液，调节PH值至8‑10之间，并维持在80℃‑100℃，搅拌反应2‑6小时；反应结束后将固体产物过滤、水洗、烘干，再置于N，N‑二甲基甲酰胺中除杂，最后经过过滤、水洗、烘干后得到白色粉末，白色粉末为专用助剂，本发明制得的专用助剂，能够使PB‑1熔融加工后转变为稳定的晶型I的时间可以缩短为36h左右，使PB‑1能够大规模生产及应用。The invention relates to a preparation method of a special auxiliary agent for improving the conversion rate of polybutene-1 crystal form and the application of the special auxiliary agent, belonging to the technical field of polymer materials, and specifically comprising adding norbornene dicarboxylic acid soap metal salt The white solid powder was dissolved in N,N-dimethylformamide and completely dissolved; the hydrochloric acid solution was slowly added dropwise, and the pH value was adjusted to between 2-5; the cellulose powder was added to the above system, and stirred to disperse Evenly; then add dropwise sodium hydroxide solution, adjust the pH value to between 8-10, and maintain at 80 ℃-100 ℃, and stir and react for 2-6 hours; after the reaction, the solid product is filtered, washed with water, and dried. , and then placed in N,N-dimethylformamide to remove impurities, and finally after filtration, washing and drying, white powder is obtained, and the white powder is a special auxiliary agent, and the special auxiliary agent prepared by the present invention can make PB- 1. The time to convert into stable crystal form I after melt processing can be shortened to about 36h, enabling large-scale production and application of PB-1.
Description
Technical Field
The invention relates to a preparation method of a special auxiliary agent for improving the crystal form conversion rate of polybutene-1 and application of the special auxiliary agent, and belongs to the technical field of high polymer materials.
Background
The polybutene-1 (PB-1) has excellent comprehensive performance and is especially suitable for hot water pipes in drinking, heating and other fields. Compared with the current domestic mainstream random copolymerization polypropylene (PP-R) pipe, the PB-1 pipe has the advantages of strong hoop stress bearing capacity, excellent creep resistance, low energy consumption, no scaling and the like after long-term use, and the construction performance is similar to that of PP-R. However, PB-1 is a polycrystalline polymer, firstly generates an unstable crystal form II after melt processing and molding, and can be converted into a stable and valuable crystal form I after 7 days at room temperature. The above disadvantages limit the wide application of iPB, which is a problem to be solved.
In recent years, researchers have made progress to accelerating the crystal transformation rate by using methods such as mixing auxiliary forming, memory ordered melting, two-step annealing and the like. However, the above methods have disadvantages that the operation is complicated and the industrial application is impossible.
Chinese patents with publication numbers CN106046573A, CN106147045A, CN105924811A and CN106147044A all report a series of applications of directly using polypropylene nucleating agent to promote the conversion rate of PB-1 crystal form. However, PB-1 in the above study was completely converted in about 44 hours, and the completion of conversion in 44 hours was far from the practical requirement.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method of a special auxiliary agent for improving the conversion rate of a polybutene-1 crystal form and an application of the special auxiliary agent, and by adding the special auxiliary agent, the time for converting PB-1 into a stable crystal form I after melt processing can be shortened to about 36h, so that the special auxiliary agent is suitable for large-scale production and application of PB-1.
In order to achieve the purpose, the technical scheme adopted by the invention is a preparation method of a special auxiliary agent for improving the crystal form conversion rate of polybutene-1, and the preparation method comprises the following steps:
s1, dissolving 5g of norbornene dicarboxylic acid soap metal salt white solid powder in 50-100ml of N, N-dimethylformamide at the temperature of 100-130 ℃ to completely dissolve the powder;
s2, slowly dripping hydrochloric acid solution with excessive concentration of 30-50% into the system in the step S1 to keep the pH value of the system between 2-5;
s3, adding 1-5g of cellulose powder with the grain diameter of 20-200 mu m into the system in the step S2, and stirring to uniformly disperse the cellulose powder;
s4, adding dropwise sodium hydroxide solution with the concentration of 30% -50% into the system in the step S3 to maintain the pH value of the system between 8 and 10, maintain the temperature of the system between 80 ℃ and 100 ℃, and stirring and reacting for 2-6 hours;
s5, after the reaction is finished, filtering, washing and drying the solid product, then placing the dried powder in 50-100ml of N, N-dimethylformamide at 130 ℃ for impurity removal, and finally filtering, washing and drying to obtain white powder, wherein the white powder is a special auxiliary agent capable of greatly improving the crystal form conversion rate of the polybutene-1.
Preferably, the structural formula of the norbornene dicarboxylic acid soap metal salt in the step S1 is
Preferably, the cellulose powder in step S3 is microcrystalline cellulose or bacterial cellulose.
The application of the special auxiliary agent for improving the crystal form conversion rate of the polybutene-1 is to uniformly mix polybutene-1 resin and 0.01 to 0.5 percent of the special auxiliary agent in a high-speed mixer, and to form the polybutene-1 crystal form by the steps of extrusion, granulation, injection molding and the like.
Preferably, the usage amount of the special auxiliary agent is 0.1%.
Compared with the prior art, the invention has the following technical effects.
1. The method has the advantages of simple operation method and simple reaction principle, and can be used for large-scale production. The norbornene dicarboxylic acid soap molecular chain is combined with the cellulose through chemical reaction by a simple method, rather than simple mixing, so that the effect of the special auxiliary agent is greatly improved.
2. During the melting process, the cellulose induces polybutene-1 to accelerate the crystal form transformation rate through heterogeneous nucleation. In addition, norbornene dicarboxylic acid soap molecules are recrystallized on the surface of cellulose to form crystals with more perfect micro-morphology, so that the conversion rate of the polybutene-1 crystal form is further accelerated.
3. Through chemical reaction, hydroxyl on a cellulose molecular chain is greatly reduced, so that the special auxiliary agent can be better dispersed in a polybutene-1 matrix, and a more excellent effect is achieved.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The starting materials, reagents and equipment used in the present invention are those conventionally commercially available in the art unless otherwise specified. Wherein PB-1 is purchased from Mitsui chemical company of Japan and has a melt index of 50-200g/10 min.
The effect of the present invention on the crystalline form conversion of polybutene-1 is further illustrated by comparing the specific examples of the present invention with comparative examples 1 and 2.
Example 1
5g of norbornene dicarboxylic acid aluminum soap salt white solid powder was dissolved in 100ml of N, N-dimethylformamide at 130 ℃. After complete dissolution, a 30% excess hydrochloric acid solution was slowly added dropwise to the mixture at room temperature, maintaining the pH of the reaction at 3. 1g of bacterial cellulose powder having a particle size of 20 μm was added to the above reaction mixture, and stirred to disperse the powder uniformly. Then, a 50% sodium hydroxide solution was added dropwise to the reaction mixture to maintain the pH of the system at 8. The reaction temperature was maintained at 80 ℃ and the reaction was stirred for 4 hours. And after the reaction is finished, filtering, washing and drying the solid product. Then the dried powder is placed in 100ml of N, N-dimethylformamide at 130 ℃ for impurity removal. And finally, filtering, washing and drying to obtain the special auxiliary white powder capable of greatly improving the PB-1 crystal form conversion rate.
0.1g of the special auxiliary agent and 1000g of PB-1 are uniformly mixed in a high-speed mixer and are molded through the steps of extrusion, granulation, injection molding and the like.
10mg of the above sample was placed in an aluminum crucible and placed in a Differential Scanning Calorimeter (DSC). DSC was set up as follows: increasing the temperature from 20 ℃ to 200 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 5min, decreasing the temperature from 200 ℃ to 20 ℃ at a cooling rate of 60 ℃/min, and finally increasing the temperature from 20 ℃ to 200 ℃. And recording the last temperature rise curve, and obtaining the melting enthalpy delta H1 of the crystal form I and the melting enthalpy delta H2 of the crystal form II of the PB-1 from the last temperature rise curve. The crystal form conversion (T) of PB-1 was determined by the following equation.
Comparative example 1
0.1g of norbornene dicarboxylic acid soap aluminum salt solid powder described in example 1 and 1000g of PB-1 were uniformly mixed in a high-speed mixer, and subjected to extrusion, granulation, injection molding and the like to mold. The samples were tested and the crystal form conversion was calculated every 12h from 0 h after molding, according to the method described above. Specific data are shown in table 1.
Comparative example 2
1000g of PB-1 is uniformly mixed in a high-speed mixer and is molded through the steps of extrusion, granulation, injection molding and the like. The samples were tested and the crystal form conversion was calculated every 12h from 0 h after molding, according to the method described above. Specific data are shown in table 1.
TABLE 1 conversion of the forms of PB-1 described in the examples and comparative examples
As can be seen from Table 1, the PB-1 material added with the special auxiliary synthesized by the invention completes the conversion from the crystal form II to the crystal form I within 36 hours after the forming. In contrast, the material of comparative example 1 was accelerated by 12 hours at 48 hours. And pure PB-1 only completes 75.89% of crystal form conversion after being placed for 48 hours, which shows that the special auxiliary synthesized by the invention has obvious effect on improving the PB-1 crystal form conversion rate and can shorten the processing period, thereby having important significance on the application of PB-1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principles of the present invention are intended to be included therein.
Claims (5)
1. A preparation method of a special auxiliary agent for improving the conversion rate of a polybutene-1 crystal form is characterized by comprising the following steps:
s1, dissolving 5g of norbornene dicarboxylic acid soap aluminum salt white solid powder in 50-100ml of N, N-dimethylformamide at the temperature of 100-130 ℃ to completely dissolve the powder;
s2, slowly dripping hydrochloric acid solution with excessive concentration of 30-50% into the system in the step S1 to keep the pH value of the system between 2-5;
s3, adding 1-5g of cellulose powder with the grain diameter of 20-200 mu m into the system in the step S2, and stirring to uniformly disperse the cellulose powder;
s4, then dropwise adding a sodium hydroxide solution with the concentration of 30-50% into the system in the step S3 to maintain the pH value of the system between 8 and 10, maintain the temperature of the system between 80 and 100 ℃, and stirring and reacting for 2 to 6 hours;
s5, after the reaction is finished, filtering, washing and drying the solid product, then placing the dried powder in 50-100ml of N, N-dimethylformamide at 130 ℃ for impurity removal, and finally filtering, washing and drying to obtain white powder, wherein the white powder is a special auxiliary agent capable of greatly improving the crystal form conversion rate of the polybutene-1.
2. The preparation method of the special additive for improving the conversion rate of the crystal form of polybutene-1 according to claim 1, wherein: the structural formula of the norbornene dicarboxylic acid soap aluminum salt in the step S1 is
。
3. The preparation method of the special additive for improving the conversion rate of the crystal form of polybutene-1 according to claim 1, wherein: the cellulose powder in the step S3 is microcrystalline cellulose or bacterial cellulose.
4. The application of the special auxiliary agent prepared by the preparation method for improving the crystal form conversion rate of polybutene-1 according to claim 1 or 2, wherein the special auxiliary agent is prepared by the following steps: the polybutene-1 resin and 0.01-0.5% of the special assistant are mixed in a high-speed mixer uniformly and are molded through the steps of extrusion, granulation and injection molding.
5. The application of the special additive for improving the conversion rate of the polybutene-1 crystal form according to claim 4, wherein: the usage amount of the special auxiliary agent is 0.1%.
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| CN114605703B (en) * | 2022-01-21 | 2023-05-19 | 太原科技大学 | A preparation method and application of a special additive for improving the heat resistance of waste polypropylene materials |
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