CN112480595A - Composite material for refrigerator partition plate and preparation method thereof - Google Patents
Composite material for refrigerator partition plate and preparation method thereof Download PDFInfo
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- CN112480595A CN112480595A CN202011419896.9A CN202011419896A CN112480595A CN 112480595 A CN112480595 A CN 112480595A CN 202011419896 A CN202011419896 A CN 202011419896A CN 112480595 A CN112480595 A CN 112480595A
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- cyclodextrin
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2312/00—Crosslinking
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the field of refrigerator partition plate materials, and particularly discloses a composite material for a refrigerator partition plate and a preparation method of the composite material. The composite material for the refrigerator partition is prepared from the following raw materials in parts by weight: 60-80 parts of ABS resin, 3-8 parts of silver nitrate, 8-15 parts of modified PAMAM dendritic polymer and 1-3 parts of lubricant; the preparation method comprises the following steps: s1, stirring the modified PAMAM dendritic polymer and a silver nitrate solution at 40-60 ℃ for 30-50min, then adding ABS resin and a lubricant to prepare a mixture, and S2, adding the mixture into an extruder, melting, extruding and cutting to prepare the composite material for the refrigerator partition. The preparation method has the advantage of reducing the possibility of brittle cracks of the separator caused by Ag ions.
Description
Technical Field
The application relates to the field of refrigerator partition plate materials, in particular to a composite material for a refrigerator partition plate and a preparation method thereof.
Background
The refrigerator is a necessary household appliance in modern families, can prevent food from rotting and prolong the shelf life of the food. Since the refrigerator is in a state of being used for a long time and stores various kinds of foods, harmful substances such as mold are inevitably generated in the refrigerator, especially at a partition for placing the foods in the refrigerating chamber. The refrigerator partition board is made of ABS resin, namely polyacrylonitrile-butadiene-styrene resin, and has the advantages of low temperature resistance and easiness in processing. However, ABS resin is easy to breed bacteria or mould in the process of processing and using as a refrigerator clapboard, and causes damage to human bodies. Therefore, the requirement on the antibacterial performance of the ABS resin used as the refrigerator partition plate is higher.
Chinese application patent publication No. CN104744875A proposes a method for preparing an antibacterial ABS material, and discloses an ABS antibacterial resin added with an antibacterial masterbatch, wherein silver ion antibacterial agent, zinc oxide or copper oxide and ABS are prepared into the antibacterial masterbatch according to a mass ratio of 10:1, so that the silver ion antibacterial agent, zinc oxide or copper oxide are effectively and uniformly dispersed in the ABS resin, thereby improving the antibacterial efficiency.
In view of the above technical solutions, the inventors consider that: when the antibacterial ABS material is used in practice, the surface of the partition board is scratched sometimes in the production, transportation and use processes, so that stress concentration of the partition board is caused, and Ag ions with strong activity enter gaps of the partition board and act on the stress concentration parts of the partition board, so that the partition board is subjected to brittle cracks.
Disclosure of Invention
In order to solve the problem that the brittle cracks of the partition plate are caused by Ag ions, the application provides a composite material for the partition plate of the refrigerator and a preparation method thereof.
In a first aspect, the present application provides a composite material for a refrigerator partition, which adopts the following technical scheme:
a composite material for a refrigerator partition is prepared from the following raw materials in parts by weight:
60-80 parts of ABS resin
3-8 parts of silver nitrate
8-15 parts of modified PAMAM dendritic polymer
1-3 parts of lubricant
The preparation method of the modified PAMAM dendritic polymer comprises the following steps:
dispersing cyclodextrin in pyridine, dropwise adding acryloyl chloride solution at 0 ℃, carrying out reduced pressure distillation to obtain a solid, fully dissolving the solid and PAMAM dendritic polymer in DMF, dialyzing, and carrying out freeze drying to obtain the modified PAMAM dendritic polymer, wherein the mass ratio of the acryloyl chloride to the cyclodextrin to the PAMAM dendritic polymer is (0.02-0.08): (0.3-0.7): 1.
by adopting the technical scheme, the modified PAMAM dendritic polymer and the ABS resin have a synergistic effect, the modified PAMAM dendritic polymer coats Ag ions, so that the Ag ions can be slowly released from the modified PAMAM dendritic polymer, the refrigerator partition plate has a continuous antibacterial effect, and the PAMAM dendritic polymer is crosslinked with cyclodextrin, so that on one hand, a channel for releasing the Ag ions is formed, the Ag ions are prevented from entering gaps of the partition plate and acting on a stress concentration region to cause the partition plate to have brittle cracks, on the other hand, the modified PAMAM dendritic polymer is crosslinked with the ABS resin, and the possibility of the partition plate having the brittle cracks after being scratched is reduced.
Preferably, the mass ratio of the acryloyl chloride to the cyclodextrin to the PAMAM dendritic polymer is (0.02-0.08): (0.3-0.7): 1.
by adopting the technical scheme, the PAMAM dendritic polymer and the cyclodextrin have good crosslinking effect, so that the composite material used for the refrigerator partition plate has good sterilization effect.
Preferably, the cyclodextrin is one or more of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
By adopting the technical scheme, the alpha-cyclodextrin, the beta-cyclodextrin and the gamma-cyclodextrin can be used as cyclodextrin raw materials.
Preferably, the cyclodextrin is β -cyclodextrin.
By adopting the technical scheme, compared with alpha-cyclodextrin and gamma-cyclodextrin, the beta-cyclodextrin has the minimum solubility in water, has the best effect of coating Ag ions after being crosslinked with PAMAM dendritic polymer, and has better sterilization effect on the composite material used for the refrigerator partition plate.
Preferably, the composite material for the refrigerator partition board is prepared from the following raw materials in parts by weight: 65-75 parts of ABS resin, 3-8 parts of silver nitrate, 8-10 parts of modified PAMAM dendritic polymer and 1-2 parts of lubricant.
By adopting the technical scheme, the impact strength of the notch of the simply supported beam made of the composite material for the refrigerator partition plate is high, and the possibility of the partition plate generating brittle cracks is low.
Preferably, the lubricant is one or more of pentaerythritol stearate, oxidized polyethylene wax and amide wax.
By adopting the technical scheme, pentaerythritol stearate, oxidized polyethylene wax and amide wax can be used as the lubricant.
In a second aspect, the present application provides a method for preparing a composite material for a refrigerator partition, which adopts the following technical scheme: the preparation method of the composite material for the refrigerator partition comprises the following steps:
s1, stirring the modified PAMAM dendritic polymer and a silver nitrate solution at 40-60 ℃ for 30-50min, and then adding ABS resin and a lubricant to prepare a mixture;
and S2, putting the mixture into an extruder, and melting, extruding and cutting to obtain the composite material for the refrigerator partition board.
By adopting the technical scheme, the PAMAM dendritic polymer and the cyclodextrin form a cross-linked network structure and are cross-linked with the ABS resin, so that the possibility of brittle cracks of the separator is further reduced.
Preferably, the modified PAMAM dendrimer is stirred with the silver nitrate solution at 50 ℃ in the S1 step.
By adopting the technical scheme, the prepared composite material for the refrigerator partition plate has good impact strength, the cross-linked net structure formed by the PAMAM dendritic polymer and the cyclodextrin has good cross-linked effect with the ABS resin, and the possibility of brittle cracks generated on the partition plate is low.
In summary, the present application has the following beneficial effects:
1. because the PAMAM dendritic polymer is modified by the cyclodextrin, the modified PAMAM dendritic polymer is crosslinked with the ABS resin, the possibility that Ag ions enter gaps of the partition board and act on a stress concentration area is reduced, and the possibility that the partition board has brittle cracks is reduced;
2. beta-cyclodextrin with the minimum solubility in water is preferably adopted in the application, the Ag ion coating effect is the best after the beta-cyclodextrin is crosslinked with PAMAM dendritic polymer, and the sterilization effect of the composite material used for the refrigerator partition plate is better.
Detailed Description
The present application is described in further detail below with reference to preparation examples and examples.
The raw material sources used in the preparation examples and the examples are shown in the following table 1:
TABLE 1 raw material sources and specifications
Preparation of modified PAMAM dendrimers
Preparation example 1
A modified PAMAM dendrimer prepared by the steps of:
dispersing 5g of alpha-cyclodextrin in 200ml of pyridine, dropwise adding 0.3g of acryloyl chloride solution at 0 ℃, carrying out reduced pressure distillation to obtain a solid, fully dissolving all the solid and 10g of PAMAM dendritic polymer 5 in 70ml of DMF solvent, heating the reaction system to 50 ℃, reacting for 40h at a constant temperature, dialyzing, and carrying out freeze drying to obtain the modified PAMAM dendritic polymer.
Preparation examples 2 to 5
Preparation examples 2 to 5 differed from preparation example 1 only in that: the weight ratio of the raw materials used was varied and is shown in Table 2.
TABLE 2 examples 1-5 raw material weight ratios
Preparation examples 6 to 8
Preparation examples 6 to 8 differed from preparation example 1 only in that: the raw materials used are different in type, and are shown in Table 3.
TABLE 3 preparation examples 6 to 8 raw material types
| Preparation example | Preparation example 1 | Preparation example 6 | Preparation example 7 | Preparation example 8 |
| Cyclodextrin | Alpha-cyclodextrin | Gamma-cyclodextrin | Beta-cyclodextrin | Beta-cyclodextrin |
| PAMAM dendrimers | PAMAM dendrimer 5 Generation | PAMAM dendrimer 5 Generation | PAMAM dendrimer Generation 1 | PAMAM dendrimer 5 Generation |
Examples
Example 1
A preparation method of a composite material for a refrigerator partition plate comprises the following steps:
s1, stirring 8g of the modified PAMAM dendritic polymer prepared in the preparation example 1 and 5g of silver nitrate solution at 40 ℃ for 30min, and then adding 60g of ABS resin 1 and 3g of pentaerythritol stearate to prepare a mixture;
and S2, putting the mixture into an extruder, melting at 200 ℃, extruding and cutting to obtain the composite material for the refrigerator partition plate.
Examples 2 to 5
Examples 2-5 differ from example 1 in that: the raw materials are different in composition and dosage, and are specifically shown in Table 4.
TABLE 4 raw material compositions and amounts for examples 1-5
Examples 6 to 8
Examples 6-8 differ from example 1 only in that: the weight of the raw materials used was varied and is shown in Table 5.
TABLE 5 examples 6-8 raw material weights
Example 9
Example 9 differs from example 1 only in that: the modified PAMAM dendrimer is stirred with the silver nitrate solution at 50 ℃ for 30min in step S1.
Examples 10 to 14
Examples 10-14 differ from example 1 only in that: the source of the modified PAMAM dendrimer used was varied and is shown in table 6.
TABLE 6 examples 10-14 sources of modified PAMAM dendrimers
| Examples | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 |
| Modified PAMAM dendrimer sources | Preparation example 4 | Preparation example 5 | Preparation example 6 | Preparation example 7 | Preparation example 8 |
Comparative example
Comparative example 1
Comparative example 1 differs from example 3 only in that: the PAMAM dendritic polymer 5 generation and the PAMAM dendritic polymer 5 generation which are equal to the alpha-cyclodextrin are fully dissolved in 30g of DMF solvent to replace the modified PAMAM dendritic polymer.
Comparative example 2
Comparative example 2 differs from example 3 only in that: equal amounts of alpha-cyclodextrin were used instead of PAMAM dendrimer for 5 passages.
Comparative example 3
Comparative example 2 differs from example 3 only in that: the modified PAMAM dendrimer was replaced with an equal amount of ABS resin 2 for 5 generations.
Comparative example 4
Comparative example 4 differs from example 3 only in that: the modified PAMAM dendrimer was replaced with an equal amount of ABS resin 2.
Performance detection
The composites for refrigerator partitions of examples 1 to 14 and comparative examples 1 to 4 were subjected to the following performance tests.
And (3) testing antibacterial performance: samples after 10, 90 and 180 days of use in the same environment were tested for antibacterial activity according to the national standard GB 21551.2-2010.
And (3) testing the impact performance of the simply supported beam notch: the impact performance of the notch of the simply supported beam is tested according to GB/T1043.1-2008, a 2J impact hammer is adopted, and the span is 40 mm.
The results of the antibacterial property tests of examples 1 to 14 and comparative examples 1 to 3 are shown in Table 7.
The results of the impact properties of the simple beam notched test of examples 1 to 14 and comparative examples 1 to 4 are shown in Table 8.
TABLE 7 antibacterial property test results of examples 1 to 14 and comparative examples 1 to 3
TABLE 8 notched impact test results for simple beams of examples 1-14, comparative examples 1-4
The analysis of the above test data shows that:
data for comparative examples 1-5: the composite material for a refrigerator partition of example 1 has the highest sterilization rate and the highest impact strength of the notch of the simply supported beam, and thus example 1 is the most preferable example of examples 1 to 5.
Comparative examples 1-3 compared to example 3, comparative example 1 differs from example 3 only in that: instead of modifying PAMAM dendrimer, which was sufficiently dissolved in 30g dmf solvent using PAMAM dendrimer 5 in the same amount as α -cyclodextrin and PAMAM dendrimer 5 in 10g, comparative example 2 differed from example 3 only in that: comparative example 3 differs from example 3 only in that, instead of PAMAM dendrimer, an equal amount of alpha-cyclodextrin was used for 5 passages: the equivalent ABS resin 2 is used for replacing the modified PAMAM dendritic polymer for 5 generations, the sterilization rate of comparative examples 1-3 after 10 days is only slightly lower than that of example 3, the sterilization rate of comparative examples 1-3 after 90 days is obviously reduced, the sterilization rate after 180 days is rapidly reduced, and the sterilization rate of example 3 after 90 days and 180 days is hardly reduced, which shows that the composite material for the refrigerator partition board has a good slow release effect on Ag ions, so that the refrigerator partition board has a continuous antibacterial effect. Comparative example 4 differs from example 3 only in that: the ABS resin 2 with the same quantity is used for replacing the modified PAMAM dendritic polymer, the notch impact strength of the simple beam of the comparative examples 1-3 is far lower than that of the simple beam of the embodiment 3, the notch impact strength of the simple beam of the comparative example 4 is not greatly different from that of the simple beam of the embodiment 3, the modified PAMAM dendritic polymer and the ABS resin have a synergistic effect, Ag ions are doped to enable the Ag ions to enter gaps of the partition plate, the possibility of brittle cracks appearing in stress concentration areas of the partition plate is increased, the Ag ions enter the gaps of the partition plate and act on the stress concentration areas to cause the possibility of the brittle cracks appearing in the partition plate is reduced by forming channels for releasing the Ag ions, and the modified PAMAM dendritic polymer is crosslinked with the ABS resin, so that the possibility of the brittle cracks appearing in the partition plate is further reduced.
Examples 6-8 compared to example 1, except that the weight of each raw material was different, the impact strength of the simple beam notch of examples 6-8 was higher than that of examples 6-8, indicating that when the composite material for the refrigerator partition is made of raw materials comprising the following parts by weight: 65-75 parts of ABS resin, 3-8 parts of silver nitrate, 8-10 parts of modified PAMAM dendritic polymer and 1-2 parts of lubricant, the impact strength of the notch of the simply supported beam is high, and the possibility of the diaphragm generating brittle cracks is low.
Compared with example 1, the difference of example 9 is that the stirring temperature in the step S1 is 50 ℃, and the impact strength of the gap of the simple beam in example 9 is higher than that in example 1, which shows that when the modified PAMAM dendritic polymer and the silver nitrate solution are stirred at 50 ℃ in the step S1, the prepared composite material for the refrigerator partition has better impact strength, the crosslinking effect of the crosslinked network structure formed by the PAMAM dendritic polymer and the cyclodextrin and the ABS resin is better, and the possibility of the partition generating brittle cracks is lower.
Examples 10-11 compared to example 1, differing only in that the modified PAMAM dendrimer of example 10 originated from preparative example 4, the modified PAMAM dendrimer of example 11 originated from preparative example 5, the bactericidal rate and the simple beam notched impact strength of examples 10-11 were both higher than those of example 1, indicating that the mass ratio of acryloyl chloride, cyclodextrin, PAMAM dendrimer was (0.04-0.05): (0.5-0.6): 1, the PAMAM dendritic polymer has better crosslinking effect with cyclodextrin.
Compared with the embodiment 1, the embodiments 13 to 14 are only different in that the cyclodextrin used in the embodiments 13 to 14 is beta-cyclodextrin, the sterilization rate and the impact strength of the simple beam notch of the embodiments 13 to 14 are higher than those of the embodiment 1, and the composite material for the refrigerator partition prepared by using the cyclodextrin is beta-cyclodextrin is better in sterilization effect.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. The composite material for the refrigerator partition is characterized by being prepared from the following raw materials in parts by weight:
60-80 parts of ABS resin
3-8 parts of silver nitrate
8-15 parts of modified PAMAM dendritic polymer
1-3 parts of lubricant
The preparation method of the modified PAMAM dendritic polymer comprises the following steps:
dispersing cyclodextrin in pyridine, dropwise adding acryloyl chloride solution at 0 ℃, carrying out reduced pressure distillation to obtain a solid, fully dissolving the solid and PAMAM dendritic polymer in DMF, dialyzing, and carrying out freeze drying to obtain the modified PAMAM dendritic polymer, wherein the mass ratio of the acryloyl chloride to the cyclodextrin to the PAMAM dendritic polymer is (0.02-0.08): (0.3-0.7): 1.
2. the composite material for a refrigerator partition according to claim 1, wherein: the mass ratio of the acryloyl chloride to the cyclodextrin to the PAMAM dendritic polymer is (0.04-0.05): (0.5-0.6): 1.
3. the composite material for a refrigerator partition according to claim 1, wherein: the cyclodextrin is one or more of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
4. A composite material for a refrigerator partition according to claim 3, wherein: the cyclodextrin is beta-cyclodextrin.
5. The composite material for a refrigerator partition according to claim 1, wherein: the feed is prepared from the following raw materials in parts by weight: 65-75 parts of ABS resin, 3-8 parts of silver nitrate, 8-10 parts of modified PAMAM dendritic polymer and 1-2 parts of lubricant.
6. The composite material for a refrigerator partition according to claim 1, wherein: the lubricant is one or more of pentaerythritol stearate, oxidized polyethylene wax and amide wax.
7. A method for preparing a composite material for a refrigerator partition as claimed in claim 1, comprising the steps of:
s1, stirring the modified PAMAM dendritic polymer and a silver nitrate solution at 40-60 ℃ for 30-50min, and then adding ABS resin and a lubricant to prepare a mixture;
and S2, putting the mixture into an extruder, and melting, extruding and cutting to obtain the composite material for the refrigerator partition board.
8. The method for preparing a composite material for a refrigerator partition according to claim 7, wherein: in step S1, the modified PAMAM dendrimer is stirred with a silver nitrate solution at 50 ℃.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140178A (en) * | 2010-12-28 | 2011-08-03 | 重庆工商大学 | Cyclodextrin-polyamidoamine cross-linked polymer and preparation method and application thereof |
| CN102728850A (en) * | 2012-06-20 | 2012-10-17 | 湖北富邦科技股份有限公司 | Method for preparing high-stability polymer coated nano silver cluster |
| CN102846654A (en) * | 2012-07-25 | 2013-01-02 | 中国人民解放军第四军医大学 | Application of polyamide amine-type dendritic polymer in preparation of medicament formed by antibacterial biofilm |
| CN103804528A (en) * | 2012-11-14 | 2014-05-21 | 中国药科大学 | New method for preparing cyclodextrin (meth)acrylate |
| CN104497231A (en) * | 2015-01-08 | 2015-04-08 | 中山大学惠州研究院 | Method for preparing modified oil-absorptive resin immobilized with cyclodextrin molecules |
| CN111718556A (en) * | 2020-06-15 | 2020-09-29 | 杭州思创磁性器件有限公司 | Antibacterial ABS material for magnetic toy and preparation method thereof |
| CN111909364A (en) * | 2020-08-11 | 2020-11-10 | 常州美胜生物材料有限公司 | Preparation method of silver-series antibacterial masterbatch |
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2020
- 2020-12-05 CN CN202011419896.9A patent/CN112480595A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140178A (en) * | 2010-12-28 | 2011-08-03 | 重庆工商大学 | Cyclodextrin-polyamidoamine cross-linked polymer and preparation method and application thereof |
| CN102728850A (en) * | 2012-06-20 | 2012-10-17 | 湖北富邦科技股份有限公司 | Method for preparing high-stability polymer coated nano silver cluster |
| CN102846654A (en) * | 2012-07-25 | 2013-01-02 | 中国人民解放军第四军医大学 | Application of polyamide amine-type dendritic polymer in preparation of medicament formed by antibacterial biofilm |
| CN103804528A (en) * | 2012-11-14 | 2014-05-21 | 中国药科大学 | New method for preparing cyclodextrin (meth)acrylate |
| CN104497231A (en) * | 2015-01-08 | 2015-04-08 | 中山大学惠州研究院 | Method for preparing modified oil-absorptive resin immobilized with cyclodextrin molecules |
| CN111718556A (en) * | 2020-06-15 | 2020-09-29 | 杭州思创磁性器件有限公司 | Antibacterial ABS material for magnetic toy and preparation method thereof |
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