CN110982241A - Polycarbonate modified plastic for extreme environmental temperature and preparation method and application thereof - Google Patents
Polycarbonate modified plastic for extreme environmental temperature and preparation method and application thereof Download PDFInfo
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- CN110982241A CN110982241A CN201911392369.0A CN201911392369A CN110982241A CN 110982241 A CN110982241 A CN 110982241A CN 201911392369 A CN201911392369 A CN 201911392369A CN 110982241 A CN110982241 A CN 110982241A
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
Abstract
The invention discloses polycarbonate modified plastic for extreme environmental temperature and a preparation method and application thereof. The polycarbonate modified plastic comprises 60-90 parts by weight of polycarbonate, 5-30 parts by weight of cold-resistant toughening agent, 0.2-0.5 part by weight of ultraviolet absorbent, 0.2-0.6 part by weight of first auxiliary agent and 0.5-2 parts by weight of second auxiliary agent. The invention has the advantages that the polycarbonate resin is subjected to the performance modification of the plastic material suitable for the extreme environment temperature (-55-70 ℃), and the prepared material not only has the impact resistance and stress crack resistance at the low temperature of-55 ℃, but also has the heat resistance and rigidity at the high temperature of 70 ℃. The military ammunition packing box prepared from the polycarbonate modified plastic can meet the test requirements of 70 ℃ at high temperature, 48h of sealing performance, 24 m high stacking, 55 ℃ below zero at low temperature, 24h of load drop and the like, and has the packing storage life of more than 20 years. The method has wide application prospect in the fields of military affairs, scientific investigation, explosion prevention and terrorism prevention, precision instruments and the like which can meet the condition of extreme environment temperature.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to a polycarbonate material, and particularly relates to polycarbonate modified plastic for extreme environments, and a preparation method and application thereof.
Background
Polycarbonate (PC) is a high molecular material, has a certain heat resistance, rigidity, and excellent notch impact resistance at normal temperature, and is also widely used in fields such as automobiles, military industry, and the like. But because the PC product is easy to stress crack when the wall thickness reaches more than 5mm, the impact resistance at low temperature, especially at-55 ℃, is obviously reduced, the ordinary toughening agent or the proportioning combination is difficult to achieve the toughening effect at the limit environment temperature, the manufactured military ammunition packing box is easy to stress crack when falling at the low temperature of-55 ℃, and a large amount of toughening agent can cause the high-temperature 70 ℃ stacking test to be inverted and stacked, thereby limiting the application range of the military ammunition packing box.
CN 104164034A discloses a flame-retardant modified plastic and a preparation method thereof. The high impact polystyrene is added with a flame retardant for toughening and modifying, and is used for military packaging products, thereby meeting the requirements of GJB4403-2002 related tests. However, the packing box used by the inventor needs to meet the high-temperature stacking test at 70 ℃, 48h and 1.2 tons and the sealing test at 70 ℃ and 48h, and the mechanical property of the material is difficult to meet the high-temperature test requirement.
CN 106905595A discloses a composite material special for military rotational molding ammunition packaging and a preparation method thereof, wherein a certain proportion of linear low-density polyethylene LLDPE, high-density polyethylene HDPE, melamine formaldehyde resin, a cross-linking agent, nano reinforcing particles and a nucleating agent are added, so that the composite material has certain performances of impact strength, high temperature resistance and the like by utilizing proper cross-linking, but the composite material does not have a dropping performance of loading 60kg at the limit temperature, and the loading stacking performance at the high temperature of 70 ℃ is difficult to meet the requirements.
For another example, CN 1916076A discloses a low temperature resistant PC/PBT plastic alloy. Particularly, the material is mainly suitable for manufacturing housings of mowers, front bumpers, instrument panels, industrial pulleys and the like which need low temperature resistance in occasions needing low temperature resistance, the lowest temperature resistance of the material is only-40 ℃, and the material cannot meet the requirement of the extreme temperature load-bearing falling performance of packing boxes.
Although the polycarbonate cold-resistant toughening modification material prepared in the prior art can generally realize high impact strength and high hardness, the polycarbonate cold-resistant toughening modification material basically belongs to a cold-resistant polycarbonate cold-resistant modification material with the temperature of-30 ℃ to-40 ℃, products are rarely involved in load falling, and the polycarbonate cold-resistant toughening modification material for extreme environments is rarely involved. There is a need to develop environmentally friendly polycarbonate modified materials to meet the material requirements for ammunition packaging.
Disclosure of Invention
The inventors have conducted intensive studies to solve at least some of the technical problems in the prior art, and have conducted intensive studies to meet the needs of scientific demonstration, to screen various polycarbonate materials, to find a toughening agent resistant to-55 ℃ and a combination thereof, and to test the matching of various combinations of the components, to prepare a polycarbonate-modified plastic for extreme environments, which greatly improves the properties of the polycarbonate-modified material, such as extreme low-temperature impact resistance, weather resistance, stress cracking resistance, and high-temperature deformation resistance. After the test, the packing box has the low temperature of-55 ℃, the load of 60kg for 24 hours, no damage and crack for 1.5 meters, and the load of 1.2 tons for stacking without crack, bulge and stack upside down at the high temperature of 70 ℃ and 48 hours. The packing box has small bulging deformation after high temperature of 70 ℃ and 48 hours, and can ensure the sealing performance of 0.02 Mpa. The present invention has been accomplished, at least in part, based on this. Specifically, the present invention includes the following.
The invention provides polycarbonate modified plastic for extreme environmental temperature, which comprises 60-90 parts by weight of polycarbonate, 5-30 parts by weight of cold-resistant toughening agent, 0.2-0.5 part by weight of ultraviolet absorbent, 0.2-0.6 part by weight of first auxiliary agent and 0.5-2 parts by weight of second auxiliary agent.
According to the plastic modified by polycarbonate at the limiting environment temperature, preferably, the polycarbonate is bisphenol A aromatic polycarbonate, and the mass melt flow rate of the polycarbonate is 6-10g/10min at 300 ℃/1.2 kg.
The plastic is modified with polycarbonate at extreme ambient temperatures according to the invention, preferably the polycarbonate has a mass melt flow rate of 8 to 13g/10min at 300 ℃/1.2 kg.
According to the plastic modified by polycarbonate at the extreme environment temperature, the cold-resistant toughening agent is preferably at least one selected from the group consisting of a methyl methacrylate-butadiene-styrene terpolymer, a copolymer formed by grafting organic siloxane on methyl methacrylate or acrylate, a thermoplastic elastomer generated by anionic polymerization of polycarbonate and organic silicon copolymer, styrene and butadiene, and an ethylene and methacrylate copolymer.
According to the plastic modified by polycarbonate at the limiting environment temperature, the siloxane content of the copolymer formed by methyl methacrylate or acrylic ester grafted organic siloxane is preferably more than 50%, and the ethylene and methacrylate copolymer contains more than 30% of methacrylate.
According to the plastic modified by polycarbonate at extreme environmental temperature, the ultraviolet absorbent is preferably benzotriazole ultraviolet absorbent.
According to the plastic modified by polycarbonate at the extreme environmental temperature, the first auxiliary agent is preferably obtained by compounding a hindered phenol antioxidant and a phosphite antioxidant in a ratio of 1:1, the hindered phenol antioxidant is selected from one or more of the group consisting of Irganox1076, Irganox1010, Irganox1098 and Irganox1024, and the phosphite antioxidant is selected from one or more of the group consisting of Irganox168, Irganox626 and antioxidant TP 80.
According to the plastic modified with polycarbonate at extreme ambient temperatures of the present invention, preferably, the second auxiliary mixture comprises a cyclic polydimethylsiloxane liquid or a polyol fatty acid ester, and a toner.
In a second aspect of the present invention, there is provided a method for preparing a plastic modified with polycarbonate at an extreme environmental temperature, comprising the steps of:
(1) mixing polycarbonate and a cold-resistant toughening agent in proportion, mixing at a high speed, adding cyclic polydimethylsiloxane liquid or polyol fatty acid ester, mixing for 3-5 minutes, sequentially adding an ultraviolet absorbent, a first auxiliary agent and toner, and mixing again to obtain a mixed material; and
(2) and (2) melting, mixing, shearing, extruding, bracing, cooling, granulating, drying and packaging the mixed material obtained in the step (1) at the temperature of 240-260 ℃ to obtain the polycarbonate modified plastic.
In a third aspect of the invention there is provided the use of the extreme ambient temperature polycarbonate modified plastics according to the first aspect in materials specific for ammunition packaging.
The polycarbonate modified plastic disclosed by the invention well solves the problem that the injection-molded packing box of the material has no damage after the material bears a load of 60kg and falls freely at a height of 1.5 m at the ultimate low temperature of-55 ℃ for 24 hours, and simultaneously meets the problems of high-temperature 70 ℃, 48-hour sealing test and 1.2-ton stacking stability. The material has excellent impact resistance, weather resistance, stress cracking resistance, high-temperature rigidity and heat resistance at extreme temperature. The material has simple processing and preparation process, can be used for injection-molded packaging products in special fields such as military industry, precision instruments and the like, and has application value and application prospect in the field of special industries.
When the polycarbonate modified plastic is used for military ammunition packing cases, the high-temperature 70 ℃ packing tightness, the stacking test requirement and the performance test requirements of low-temperature-55 ℃ extreme cold environment load falling and the like can be simultaneously met, the existing polycarbonate material is difficult to meet the low-temperature performance requirement, and the existing polycarbonate or PC/ABS alloy modified material used in the automobile industry is difficult to meet the low-temperature performance requirement. The polycarbonate modified plastic for the extreme environment temperature has good weather resistance and simple processing and preparation process, and can be used for injection-molded packaging products in special fields such as military, precise instruments and the like. The material has a packaging storage life of more than 20 years, and has wide application prospects in the fields of military, precision instruments and the like.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that the upper and lower limits of the range, and each intervening value therebetween, is specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control. Unless otherwise indicated, "%" is percent by weight.
[ polycarbonate-modified Plastic ]
In a first aspect of the present invention, a polycarbonate-modified plastic is provided. The PC modified plastic is a polycarbonate material used for extreme environmental temperature, and the purpose is achieved by fixing the proportion of polycarbonate and other components.
The polycarbonate of the invention is medium-viscosity resin, the high viscosity is not beneficial to injection molding, and the low-viscosity resin has poor impact resistance. Preferably, the polycarbonate of the present invention is a medium viscosity UV blocking polycarbonate resin suitable for use in the composition preparation process of the present invention, and has a mass melt flow rate of 8 to 13g/10min at 300 ℃/1.2kg, more preferably, a mass melt flow rate of 8 to 10g/10 min.
The polycarbonate in the present invention is 60 to 90 parts by weight, preferably 70 to 85 parts by weight, and more preferably 77 to 85 parts by weight. The polycarbonate plastics of the invention can be synthesized by known methods or can be purchased from known commercial products. For example by means of bisphenolsA is obtained by phosgene synthesis through a solvent method or ester exchange synthesis of bisphenol A ester and diphenyl carbonate. Examples of such products are exemplified by products of the American general-purpose company, model No. PC 141R or products of the German Corseiki company, model No. PC 2805, in which the density of the viscosity ultraviolet-shielding polycarbonate resin is from 1.18 to 1.20g/cm3The molding shrinkage is 0.5-0.8%, and the molding temperature is 230-320 ℃.
The cold-resistant toughening agent of the invention is a copolymer of a specific type, and has a core-shell toughening structure, on one hand, the toughening agent is favorably combined and dispersed with PC resin (the shell belongs to esters and is favorably compatible and dispersed with the PC resin), and on the other hand, the toughening agent of the invention has a core structure of low-temperature buffering rubber pellets (such as butadiene, organic siloxane and the like). The toughening agents used by each type or a certain enterprise have different extreme low-temperature impact resistance, even one toughening agent has difficulty in achieving good effect, and various tests and combinations are required. The parts by mass should be preferred by tests and tests.
In certain embodiments, the cold resistant toughener is a terpolymer of methyl methacrylate, vinyl ethylene and styrol, which has a common core-shell structure, examples of such products are exemplified by the product number EM500A from LGChem. Considering that the common terpolymer is easy to generate phase separation, and the unstable performance of the later-period material can be caused by the uneven coating of the shell layer monomer. Therefore, in another embodiment, the cold-resistant toughening agent is a copolymer formed by methyl methacrylate, acrylic acid and ester of homologous compound thereof and organic siloxane, the shell layer of the cold-resistant toughening agent is uniformly wrapped, the balance torque is reduced, the viscosity is reduced, the melt fluidity is improved, the medium-viscosity ultraviolet-proof polycarbonate resin is combined to produce beneficial effects, and the obtained PC plastic has better impact resistance, aging resistance and lower temperature requirement. In other embodiments, the cold resistant toughener of the present invention can also be a silicon-containing polycarbonate powder. The cold-resistant toughening agent in the PC plastic is 5-30 parts by weight, preferably 5-20 parts by weight, and more preferably 5-18 parts by weight.
In the polycarbonate-modified plastic of the present invention, the ultraviolet absorber may be a benzotriazole-based ultraviolet absorber. Preferably, such an ultraviolet absorber may be exemplified by UV-234 or UV-5411. Although the PC used in the present invention is stable to light, it is not resistant to violet light. Therefore, the PC material can easily absorb ultraviolet light outdoors to initiate autoxidation reaction, which leads to degradation of the polymer and greatly reduces the physical and mechanical properties. The addition of the UV absorbers described herein thus reduces the damage to the synthesized PC material due to UV radiation, and such UV absorbers have the advantages of better solubility, a wider UV absorption range, low toxicity and inexpensive price. The ultraviolet absorber of the present invention is 0.2 to 0.5 part by weight, preferably 0.2 to 0.4 part by weight, and more preferably 0.3% part by weight.
The first auxiliary agent is a thermal aging auxiliary agent, and is obtained by compounding. Preferably, the antioxidant is obtained by compounding a hindered phenol antioxidant and a phosphite antioxidant. Hindered phenolic antioxidants are known commercial products and examples of such products are exemplified by the BASF SE company model Irganox1076, Irganox1010, Irganox1098 and Irganox 1024. Phosphite antioxidants are known commercial products, and examples of such products are exemplified by the BASF SE company, model Irganox168, Irganox626 and the antioxidant TP 80. These antioxidants trap the radicals R.and ROO.formed during the chain reaction, so that they do not cause destructive chain reactions, considering that there may be synergies or antagonisms between different types, even between the same type and different species of antioxidants. Therefore, the ratio of hindered phenol antioxidant to phosphite antioxidant in the first aid of the present invention is important when the second aid described below is determined in terms of the weight fraction of PC plastic. The inventor finds that through intensive research, the product performance can be synergistically improved and the antioxidant effect can be enhanced by compounding Irganox1076 and Irganox168, particularly when the compounding ratio is 1:1, the cost can be reduced, and obvious anti-synergistic effect can be generated by singly using one of the Irganox1076 and the Irganox168, namely, the aging of the synthesized PC plastic is accelerated and the stability of the synthesized PC plastic is influenced. Preferably, the compounded thermal aging auxiliary agent is 0.2-0.6 part by weight, and still preferably 0.4-0.5 part by weight.
In the present invention, the second auxiliary mixture comprises a cyclic polydimethylsiloxane liquid or a polyol fatty acid ester, and a toner. The toner is not particularly limited and may be selected according to color. The lubricant is not particularly limited as long as it has the same effect as the dispersant, that is, it can disperse the toner, the ultraviolet absorber, and the first aid more effectively by the lubricant and improve the processability of the material in extrusion granulation and injection molding. The lubricant may be a cyclic polydimethylsiloxane and/or a polyol fatty acid ester, and examples of such products are exemplified by products of 69 series manufactured by euro ceras corporation, for example. Since the crystalline material has a certain tolerance to fatty substances, but its amorphous region absorbs lubricating oil to cause swelling, long-term contact with the lubricating oil should be avoided. In the PC plastic, the second auxiliary mixture is 0.5-2 parts by weight. Preferably 1 to 1.5 parts by weight, more preferably 1.2 to 1.5 parts by weight.
[ production method ]
In a second aspect of the invention, a process for the preparation of plastics modified with polycarbonate at extreme ambient temperatures is provided, sometimes referred to herein simply as "the process of the invention". Specifically, the preparation method at least comprises the following steps:
(1) weighing the components according to the proportion of the first aspect, mixing the polycarbonate, the toughening agent and the cyclic polydimethylsiloxane liquid or the polyol fatty acid ester in the components at a high speed for 3-5 minutes, then sequentially adding the ultraviolet absorbent, the first auxiliary agent and the toner, and mixing for 3-10 minutes again to obtain a mixed material;
(2) and (2) melting, mixing, shearing, extruding, bracing, cooling, granulating, drying and packaging the mixed material obtained in the step (1) at the temperature of 240-260 ℃ to obtain the polycarbonate modified plastic.
Step (1) of the present invention is a mixing step using each component. In the production method of the present invention, the apparatus for carrying out high-speed mixing is not particularly limited, and the specific conditions for high-speed mixing are not particularly limited and can be freely set by those skilled in the art. Preferably, the PC-based material is mixed with the lubricant for a period of 3 to 5 minutes using a high speed mixer. The mixing time is 3-10 minutes after the other components are added in sequence. The adding sequence is important, and the ultraviolet absorbent, the thermal oxidation aging auxiliary agent and the toner are added in sequence to ensure the stability of the performance of the PC synthetic material.
In the step (2), preferably, the mixed material is added into a phi 50 and L/D-40 twin-screw extrusion bin, and the plastic modified by polycarbonate at the limit environmental temperature is obtained through melting, extrusion, granulation and drying at 240-260 ℃. The process conditions are important, and particularly, the PC-based material has high Mohs hardness, and bubbles are easily generated in the production process to influence the appearance and the material performance. Considering that the ratio of L/D of the screw is selected according to the viscosity of the mixed material during the screw processing, the L/D of the present invention is preferably 40. The melting temperature is preferably from 240 ℃ to 260 ℃ and is determined taking into account the following influencing factors: a. the formula comprises the following components in percentage by mass: the large difference in extrusion temperature for different components, doses and masses, which is unpredictable without experimental conditions or production experience; b. the energy required for converting the solid in unit volume into the solid is relatively constant, the conveying speed of the mixed material is basically balanced with the melting speed of the material, the heat required for melting the material is different due to different conveying speeds of the material, and for a heating area of the double-screw extruder with internal heat, the extrusion speed can directly influence the melting speed of the material due to the action of the internal heat; and c, the PC material extrusion time and the correct temperature time need to know the form, the temperature bearing degree and the heat requirement condition of the PC material at different extrusion stages. Based on the consideration, in the preparation process, after multiple experiments and production, the double-screw extruder is determined to be phi 50, L/D is 40, and the melting temperature condition is 240-260 ℃. Under the condition, the prepared PC material has good shape and excellent performance compared with other PC synthetic materials.
It will be appreciated by those skilled in the art that other steps or operations, such as further optimization and/or improvement of the methods described herein, may be included before or after steps (1) - (2) above, or between any of these steps, as long as the objectives of the present invention are achieved.
[ application ]
In a third aspect of the invention, there is provided the use of a polycarbonate-modified plastic according to the first aspect or obtained by the method of manufacture according to the second aspect in ammunition packaging.
Example 1
Weighing the components in percentage by mass as shown in table 1, wherein the preparation method comprises the following steps:
(1) weighing PC resin or silicone PC resin and cold-resistant toughening agent according to a ratio, adding into a high-speed mixer pot, adding cyclic polydimethylsiloxane liquid or polyol fatty acid ester, mixing for 3-5 minutes, then sequentially adding metered ultraviolet absorbent, thermal-oxidative aging auxiliary agent and toner, mixing for 3-10 minutes, and discharging after fully and uniformly mixing.
(2) And (2) adding the mixture obtained in the step (1) into a phi 50 and L/D (L/D) 40 double-screw extrusion bin, melting, mixing, shearing, extruding and bracing various materials in a charging barrel of an extruder at 240-260 ℃, cooling, granulating, drying and packaging to obtain the polycarbonate modified plastic for the extreme environment temperature.
(3) Standard GB A type samples and strip samples were prepared for testing by an injection molding machine, and the test results are shown in Table 4.
TABLE 1 compositions and amounts of polycarbonate-modified plastics
Example 2
Polycarbonate-modified plastics were produced in a similar manner to example 1 except that the composition of each ingredient was changed as shown in Table 1, and the test results thereof are shown in Table 4.
TABLE 2 compositions and amounts of different types of polycarbonate-modified plastics
| Components | Content (mass%) |
| Medium viscosity PC resin | 57.7 |
| Cold-resistant toughening agent MBS (number 2) | 10 |
| Silicon PC resin (EXL9330) | 30 |
| Ultraviolet absorber | 0.3 |
| Composite antioxidant | 0.5 |
| Toner and other auxiliaries | 1.5 |
Example 3
Polycarbonate-modified plastics were produced in a similar manner to example 1 except that the composition of each ingredient was changed as shown in tables 1 and 2, and the test results thereof are shown in table 4.
TABLE 3 compositions and amounts of different types of polycarbonate-modified plastics
| Components | Content (mass%) |
| Medium viscosity PC resin | 72.7 |
| Cold-resistant toughener siloxanes | 25 |
| Ultraviolet absorber | 0.3 |
| Thermo-oxidative aging aid | 0.5 |
| Toner and other auxiliaries | 1.5 |
Test example 1
1. Determination of tensile Strength
The tensile properties were measured according to the measurement standards of GB/T1040-2018.
2. Determination of elongation at Break
The determination was carried out according to the determination standard for elongation at break in GB/T1040-2018.
3. Measurement of bending Strength
The flexural strength was measured according to the measurement standard in GB/T9341-2008.
4. Flexural modulus measurement
The flexural modulus was measured according to the measurement standard in GB/T9341-2008.
5.23/50 notched impact Strength measurement
The notched impact strength was measured according to the test standard in GB/T1843-2008.
6. Determination of notched impact strength at-55 DEG C
The notched impact strength was measured according to the test standard in GB/T1843-2008.
Determination of deformation temperature under load of 7.1.8MPa
The measurement was carried out in accordance with the measurement standard for the load deformation temperature in GB/T1643-2004.
The specific performance test results are shown in table 4, and it can be seen from the test results that the polycarbonate modified plastic prepared by the invention has excellent impact performance at-55 ℃, heat resistance at 70 ℃ and rigidity, and has weather resistance, stress cracking resistance, thermal aging resistance and other properties and good injection molding processability. In addition, the high low-temperature impact strength in the surface cannot represent the packaging performance in low-temperature falling, and the high low-temperature impact strength is the embodiment of the comprehensive performance of the material.
TABLE 4 Performance test results for different types of polycarbonate-modified plastics
| Test items | Test standard | Unit of | Example 1 | Example 2 | Example 3 |
| Tensile strength | GB 1040 | MPa | 61 | 53 | 52.2 |
| Elongation at break | GB 1040 | ％ | 87 | 76 | 67 |
| Bending strength | GB 9341 | MPa | 65 | 60.3 | 60.2 |
| Flexural modulus | GB 9341 | MPa | 2120 | 2020 | 2050 |
| 23/50 notched impact strength | GB 1843 | kJ/m2 | 54 | 53 | 50 |
| Notched impact strength at-55 DEG C | GB 1843 | kJ/m2 | 35 | 40 | 45 |
| 1.8MPa load deformation temperature | GB 1634 | ℃ | 124 | 118 | 120 |
| Low temperature drop performance of package | Test completeness | ％ | 95％ | 100％ | 100％ |
Comparative example 1
Polycarbonate plastics were produced in a similar manner to example 1 except that the type of PC resin was changed as shown in Table 1, where a PC resin having a high melt index was used, and the test results are shown in Table 7.
TABLE 5 composition and amounts of different types of polycarbonate plastics
| Components | Content (mass%) |
| PC resin (high melt index) | 89.7 |
| Cold-resistant flexibilizer MBS | 8 |
| Ultraviolet absorber | 0.3 |
| Composite antioxidant | 0.5 |
| Toner and other auxiliaries | 1.5 |
Comparative example 2
Polycarbonate plastics were produced in a similar manner to example 1 except that the type of PC resin was changed as shown in Table 1, wherein the polycarbonate substrate used was a PC/ABS alloy material, and the test results thereof are shown in Table 7.
TABLE 6 composition and amounts of different types of polycarbonate plastics
| Components | Content (mass%) |
| PC resin | 58.4 |
| ABS resin | 24.3 |
| Cold-resistant flexibilizer MBS | 15 |
| Ultraviolet absorber | 0.3 |
| Composite antioxidant | 0.5 |
| Toner and other auxiliaries | 1.5 |
Test example 2
The polycarbonate-modified plastics prepared in comparative examples 1 and 2 were subjected to the measurements of tensile strength, elongation at break, flexural strength, flexural modulus, 23/50 notched impact strength, notched impact strength at-55 ℃ and load deflection temperatures at 1.8MPa in the same manner as in test example 1
The specific performance test results are shown in table 7, and it can be seen from the test results that the cold-resistant toughened modified material of the PC material, which is more common at present, is adopted in comparative example 1, so that the impact at the low temperature of-30 ℃ can be resisted. Because the PC resin is low-viscosity resin, the material is easy to flow and process, and the appearance of the product has good luster; the cold-resistant toughening agent is single in selection, some toughening agents have no toughening effect at-55 ℃, the low-temperature impact strength of the modified material is low, the good low-temperature falling effect is difficult to achieve, and the falling is not qualified by 50%.
The modified material of the comparative example 2 adopts a PC/ABS cold-resistant toughening modified material commonly used in the automobile industry, the ABS resin is added, the material cost is reduced, the material fluidity is good, and the requirement of the automobile industry on a cold-resistant environment at-30 ℃ can be met, but the selection requirement of the material resin and the cold-resistant toughening agent is not high, although the average value of the material impact is very high, the impact dispersion of the material is large, the comprehensive performance is difficult to meet the requirement of load falling at-55 ℃, the material is easy to crack when falling at an angular edge, and 50% of the material is unqualified when falling, so that the matching of the PC main material selection and the toughening.
TABLE 7-results of the property tests on different types of polycarbonate plastics in comparative examples
| Test items | Test standard | Unit of | Comparative example 1 | Comparative example 2 |
| Tensile strength | GB 1040 | MPa | 59 | 52 |
| Elongation at break | GB 1040 | ％ | 100 | 97 |
| Bending strength | GB 9341 | MPa | 78 | 73 |
| Flexural modulus | GB 9341 | MPa | 2100 | 1900 |
| 23/50 notched impact strength | GB 1843 | kJ/m2 | 53 | 56 |
| Notched impact strength at-55 DEG C | GB 1843 | kJ/m2 | 12 | 36 |
| 1.8MPa load deformation temperature | GB 1634 | ℃ | 124 | 120 |
| Low temperature drop performance of package | Test completeness | ％ | 50％ | 50％ |
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Many modifications and variations may be made to the exemplary embodiments of the present description without departing from the scope or spirit of the present invention. The scope of the claims is to be accorded the broadest interpretation so as to encompass all modifications and equivalent structures and functions.
Claims (10)
1. The polycarbonate modified plastic for the extreme environmental temperature is characterized by comprising 60-90 parts by weight of polycarbonate, 5-30 parts by weight of cold-resistant toughening agent, 0.2-0.5 part by weight of ultraviolet absorbent, 0.2-0.6 part by weight of first auxiliary agent and 0.5-2 parts by weight of second auxiliary agent.
2. The plastic modified with polycarbonate for extreme environmental temperatures according to claim 1, wherein the polycarbonate is a bisphenol A aromatic polycarbonate having a mass melt flow rate of 6 to 10g/10min at 300 ℃/1.2 kg.
3. The extreme environment temperature polycarbonate-modified plastic as claimed in claim 1, wherein the polycarbonate has a mass melt flow rate of 8 to 13g/10min at 300 ℃/1.2 kg.
4. The plastic modified by polycarbonate at extreme environmental temperature according to claim 1, wherein the cold-resistant toughening agent is at least one selected from the group consisting of a methyl methacrylate-butadiene-styrene terpolymer, a copolymer formed by grafting organic siloxane on methyl methacrylate or acrylate, a thermoplastic elastomer formed by anionic polymerization of polycarbonate and organic silicon copolymer, styrene and butadiene, and a copolymer of ethylene and methacrylate.
5. The plastic modified by polycarbonate for limiting ambient temperature according to claim 4, wherein the copolymer of methyl methacrylate or acrylate-based graft organosiloxane has a siloxane content of 50% or more, and the copolymer of ethylene and methacrylate contains 30% or more of methacrylate.
6. The extreme environment temperature polycarbonate-modified plastic as claimed in claim 1, wherein the ultraviolet absorber is a benzotriazole-based ultraviolet absorber.
7. The plastic modified by polycarbonate at the extreme environmental temperature according to claim 1, wherein the first auxiliary agent is obtained by compounding a hindered phenolic antioxidant and a phosphite antioxidant in a ratio of 1:1, the hindered phenolic antioxidant is one or more selected from the group consisting of Irganox1076, Irganox1010, Irganox1098 and Irganox1024, and the phosphite antioxidant is one or more selected from the group consisting of Irganox168, Irganox626 and antioxidant TP 80.
8. The extreme ambient temperature polycarbonate-modified plastic of claim 1, wherein the second auxiliary mixture comprises a cyclic polydimethylsiloxane liquid or a polyol fatty acid ester, and a toner.
9. A preparation method of polycarbonate modified plastic for limiting ambient temperature is characterized by comprising the following steps:
(1) weighing polycarbonate and a cold-resistant toughening agent according to a proportion, mixing at a high speed, adding cyclic polydimethylsiloxane liquid or polyol fatty acid ester, mixing for 3-5 minutes, then sequentially adding an ultraviolet absorbent, a first auxiliary agent and toner, and mixing again to obtain a mixed material; and
(2) and (2) melting, mixing, shearing, extruding, bracing, cooling, granulating, drying and packaging the mixed material obtained in the step (1) at the temperature of 240-260 ℃ to obtain the polycarbonate modified plastic.
10. Use of the extreme ambient temperature polycarbonate modified plastic according to any of claims 1-8 in materials specific for ammunition packaging.
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