CN111286132B - Ultrahigh molecular weight polyethylene toughened and reinforced syndiotactic polystyrene composite material and preparation method thereof - Google Patents
Ultrahigh molecular weight polyethylene toughened and reinforced syndiotactic polystyrene composite material and preparation method thereof Download PDFInfo
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- CN111286132B CN111286132B CN202010292750.6A CN202010292750A CN111286132B CN 111286132 B CN111286132 B CN 111286132B CN 202010292750 A CN202010292750 A CN 202010292750A CN 111286132 B CN111286132 B CN 111286132B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
Abstract
The invention provides an ultra-high molecular weight polyethylene toughening and reinforcing syndiotactic polystyrene composite material and a preparation method thereof, wherein the composite material mainly comprises syndiotactic polystyrene resin, ultra-high molecular weight polyethylene resin, a compatilizer, an antioxidant, a lubricant, organic peroxide and a monomer; wherein the molecular weight of the ultra-high molecular weight polyethylene resin is 250-350 ten thousand. Compared with the traditional reinforced material, the composite material of the invention has higher toughness and higher toughness than the toughened material, and can be widely applied to connecting parts and the like in the fields of electronic appliances, aviation and the like.
Description
Technical Field
The invention belongs to the field of synthesis of high polymer materials, and particularly relates to an ultrahigh molecular weight polyethylene toughened and reinforced syndiotactic polystyrene composite material and a preparation method thereof.
Background
The ultra-high molecular weight polyethylene is unbranched linear polyethylene with the molecular weight of more than 150 ten thousand, has super wear resistance and self-lubricating property, has higher strength, stable chemical property, strong ageing resistance and good impact resistance effect, and is widely applied. However, ultra-high molecular weight polyethylene has extremely high viscosity and extremely poor flowability in a molten state due to its extremely high molecular weight, and its melt index is almost zero, so that it is difficult to process it by a general machining method.
The syndiotactic polystyrene resin (SPS) has the structure of styrene arranged in the same interval and belongs to crystal polymer, and has the basic features of traditional polystyrene, heat resistance, chemical resistance, etc. and cheap material. Although syndiotactic polystyrene resin has the characteristics which common polystyrene (atactic polystyrene) does not have, the molecular chain is still a rigid chain segment which is composed of all styrene monomers, so that the syndiotactic polystyrene resin has obvious brittleness and the use environment is limited.
Disclosure of Invention
An object of the present invention is to provide an ultra-high molecular weight polyethylene toughened and reinforced syndiotactic polystyrene composite material and a preparation method thereof, so as to solve at least one of the above-mentioned problems of the prior art.
According to one aspect of the invention, the invention provides an ultrahigh molecular weight polyethylene toughened and reinforced syndiotactic polystyrene composite material, which mainly comprises syndiotactic polystyrene resin, ultrahigh molecular weight polyethylene resin, a compatilizer, an antioxidant, a lubricant, organic peroxide and a monomer; wherein the molecular weight of the ultra-high molecular weight polyethylene resin is 250-350 ten thousand.
The composite material of the invention has higher toughness than the traditional reinforced material and higher toughness than the toughened material, and can be widely applied to connecting parts in the fields of electronic appliances, aviation and the like.
In some embodiments, the ultrahigh molecular weight polyethylene toughened and reinforced syndiotactic polystyrene composite material comprises, by mass, 56.4-72.6 parts of syndiotactic polystyrene resin, 20-30 parts of ultrahigh molecular weight polyethylene resin, 5-8 parts of a compatilizer, 1-2 parts of an antioxidant, 1-3 parts of a lubricant, 0.3-0.45 part of an organic peroxide and 0.1-0.15 part of a monomer.
In some embodiments, the molecular weight of the syndiotactic polystyrene resin in the ultra-high molecular weight polyethylene toughened and reinforced syndiotactic polystyrene composite material of the present invention is 8 to 12 ten thousand. The syndiotactic polystyrene with the molecular weight range is convenient to process, the reinforcing and toughening effects of the ultra-high molecular weight polyethylene are obvious, the application range of the syndiotactic polystyrene for reducing the molecular weight is limited, and the processing difficulty is increased when the molecular weight is too high.
The invention also aims to provide a preparation method of the ultrahigh molecular weight polyethylene toughened and reinforced syndiotactic polystyrene composite material, which comprises the following steps:
mixing the ultra-high molecular weight polyethylene resin, the organic peroxide, the monomer, the lubricant, the syndiotactic polystyrene resin, the compatilizer and the antioxidant to obtain a mixture;
adding the mixture into a main feeding port of a double-screw extruder, and processing at 240-280 ℃ to obtain the ultra-high molecular weight polyethylene reinforced and toughened syndiotactic polystyrene composite material.
The invention also provides another preparation method of the ultrahigh molecular weight polyethylene toughened and reinforced syndiotactic polystyrene composite material, which comprises the following steps:
mixing the ultra-high molecular weight polyethylene resin, the organic peroxide, the monomer and the lubricant to obtain a first mixture;
mixing the syndiotactic polystyrene resin, the compatilizer and the antioxidant to obtain a second mixture;
adding the first mixture into the main feeding port of a double-screw extruder, adding the second mixture into the side feeding port of the double-screw extruder, and processing at 240-280 ℃ to obtain the ultra-high molecular weight polyethylene reinforced and toughened syndiotactic polystyrene composite material. The components are added through double feeding ports, the main feeding port performs grafting reaction on the ultrahigh molecular weight polyethylene and the monomer, and the side feeding port is added with syndiotactic polystyrene compatilizer and other components to complete blending modification.
In some embodiments, wherein the twin screw extruder has a screw length to diameter ratio of 52:1 or 56: 1. If the length-diameter ratio of the screw of the double-screw extruder is too small, the effect of grafting the ultrahigh molecular weight polyethylene and the monomer is not obvious, the compatibility with the syndiotactic polystyrene is poor, and if the length-diameter ratio of the screw of the double-screw extruder is too large, the molecular weight of the material is seriously reduced under the shearing action, the performance loss is large, the processing energy consumption is improved, and the cost is increased.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of protection to these examples.
Example 1:
20kg of ultra-high molecular weight polyethylene resin, 0.3kg of dicumyl peroxide (DCP), 0.1kg of maleic anhydride, 0.5kg of lubricant pentaerythritol stearate (PETS) and 0.5kg of calcium stearate are mixed to obtain a first mixture.
72.6kg of syndiotactic polystyrene resin, 5kg of compatilizer maleic anhydride grafted syndiotactic polystyrene, AO-800.5kg of antioxidant and 6260.5kg of antioxidant are mixed to obtain a second mixture.
And adding the first mixture into the first mixture from a main feeding port of a double-screw extruder, adding the second mixture into a side feeding port of the double-screw extruder, and processing at 260 ℃ to obtain the ultrahigh molecular weight polyethylene reinforced and toughened syndiotactic polystyrene composite material.
In the present embodiment, the molecular weight of the ultra-high molecular weight polyethylene resin is 300 ten thousand. In other embodiments, the ultra-high molecular weight polyethylene resin may have a molecular weight of 250 to 350 ten thousand
In this example, the twin-screw extruder had a screw length to diameter ratio of 52: 1. In other embodiments, the twin screw extruder may also have a screw length to diameter ratio of 56: 1.
In this example, dicumyl peroxide (DCP) was used as the organic peroxide. In other embodiments, Benzoyl Peroxide (BPO) and the like may also be used as the organic peroxide.
In this example, Maleic Anhydride (MAH) was used as the monomer. In other embodiments, acrylates (such as glycidyl acrylate GMA) and the like may also be used as the monomer.
In this example, a combination of pentaerythritol stearate (PETS) and calcium stearate (CaSt) was used as the lubricant. In other embodiments, the lubricant may be one or a combination of two or more of a silicone compound (silicone), Polytetrafluoroethylene (PTFE) having a molecular weight of 5000-.
In this example, maleic anhydride was used as the compatibilizer to graft syndiotactic polystyrene. In other embodiments, the compatibilizer may also be an ethylene acrylic acid (acrylate) copolymer and maleic anhydride grafts thereof, or glycidyl acrylate grafts, etc.
In this example, the antioxidant used was a combination of the antioxidant AO-80 and the antioxidant 626. In other examples, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (antioxidant 1098), N-octadecyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), 2- (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methyl-6-tert-butylphenyl acrylate (antioxidant 3052), 3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1, 3, 5-triazine-2, 4, 6- (1H, 3H, 5H) -trione (antioxidant 1790), and mixtures thereof, One or a combination of two or more of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (antioxidant S-9228), bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite; one or a combination of two or more of bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite is preferred.
The tensile strength of the product prepared in example 1 was found to be 38.1MPa, the notched impact strength was found to be 17.5KJ/m2, and the compatibility was found to be good.
The compatibility judging method comprises the following steps: the material was formed into a test piece of 100 mm. times.100 mm. times.3 mm, which was repeatedly folded in half ten times to see whether or not there was surface peeling at the folded position. The compatibility is poor if the folded position has surface peeling, and the compatibility is good if the folded position has no surface peeling.
Examples 1-10 in table 1 the same procedure as in example 1 was used to prepare ultra-high molecular weight polyethylene toughened and reinforced syndiotactic polystyrene composites, the amounts of polyethylene and syndiotactic polystyrene, and the types and amounts of peroxide, monomer, lubricant and compatibilizer are listed, and the test results of the prepared composites are also included. Wherein, the length-diameter ratio of the screw of the double-screw extruder adopted in the embodiments 1 to 5 is 52:1, and the length-diameter ratio of the screw of the double-screw extruder adopted in the embodiments 6 to 10 is 56: 1.
Example 11:
20kg of ultra-high molecular weight polyethylene resin, 0.3kg of dicumyl peroxide (DCP), 0.1kg of maleic anhydride, 0.5kg of lubricant pentaerythritol stearate (PETS), 0.5kg of calcium stearate, 72.6kg of syndiotactic polystyrene resin, 5kg of compatilizer maleic anhydride grafted syndiotactic polystyrene, AO-800.5kg of antioxidant and 6260.5kg of antioxidant are mixed to obtain a mixture.
Adding the mixture into a main feeding port of a double-screw extruder, and processing at 260 ℃ to obtain the ultrahigh molecular weight polyethylene reinforced and toughened syndiotactic polystyrene composite material.
Examples 11 to 20 in table 2 were prepared by the same method as in example 11, and the charging amounts of polyethylene and syndiotactic polystyrene, the types and charging amounts of peroxide, monomer, lubricant and compatilizer are listed, and the test results of the prepared composites are also included. All of the components in the examples in Table 2 were fed from the main feed port of the twin screw extruder as described in example 11. The components in the examples in Table 1 were fed separately from the main and side feed ports of the twin screw extruder, as described in example 1.
As can be seen from the comparison of the examples in Table 1 and Table 2, the composite material of ultra-high molecular weight polyethylene toughened and reinforced syndiotactic polystyrene prepared by adding the components through two feeding ports has better tensile strength and notch impact strength than the composite material prepared by adding the components through a single feeding port.
Examples 21 to 30 in table 3 were prepared by the same method as in example 1, and the feeding amounts of polyethylene and syndiotactic polystyrene, the types and feeding amounts of peroxide, monomer and lubricant, and the test results of the prepared composite materials are also included. The examples in table 3 differ from the examples in table 1 in that there is no compatibilizer, the tensile strength and impact strength of the resulting product are significantly lower than those in table 1, and the compatibility is poor, indicating that the compatibilizer has a significant effect on the compatibility of the two.
Examples 31-40 in Table 4 were prepared by the same method as in example 1, and the feeding amounts of polyethylene and syndiotactic polystyrene, the types and feeding amounts of lubricant and compatilizer, and the test results of the prepared composites are also included. The examples in table 4 are different from the examples in table 1 in that no peroxide and no monomer are added in the components, the tensile strength and impact strength of the prepared product are obviously lower than those of the products in table 1, and the compatibility is poor, which indicates that the peroxide and the monomer play a significant role in the compatibility effect of the two.
Examples 41 to 50 in Table 5 are syndiotactic polystyrene composites without the addition of ultra high molecular weight polyethylene, the amounts of syndiotactic polystyrene, the types and amounts of lubricant and compatibilizer, and the test results for the composites prepared are listed. The tensile strength and the impact strength of the prepared product are obviously lower than those of the product in the table 1, and the partial example after being folded in half has the phenomena of fracture and cracking, which indicates that the reinforcing and toughening effect source of the syndiotactic polystyrene is the ultrahigh molecular weight polyethylene.
Examples 51-60 in Table 6 were prepared by the same method as in example 1, and the feeding amounts of polyethylene and syndiotactic polystyrene, the types and feeding amounts of peroxide, monomer, lubricant and compatilizer, and the test results of the prepared composites are also included. The examples in Table 6 are different from those in Table 1 in that the screw extruders of examples 51 to 55 have an aspect ratio of 40: 1 and the screw extruders of examples 56 to 60 have an aspect ratio of 64: 1.
The tensile strength and impact strength of the products prepared in the examples in Table 6 are obviously lower than those of the products prepared in Table 1, the compatibility of the products in examples 51-55 is poor, and the products in examples 56-60 are obviously cracked after being folded in half. As described above, when the length-to-diameter ratio of the screw extruder of the present invention is 52:1 or 56:1, the mechanical properties such as tensile strength and impact strength of the composite material prepared are superior to those of the composite material prepared by using the screw extruder of the present invention in which the length-to-diameter ratio is greater or less than that of the composite material.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.
Claims (6)
1. The ultra-high molecular weight polyethylene toughened and reinforced syndiotactic polystyrene composite material is characterized in that the preparation method comprises the following steps:
mixing the ultra-high molecular weight polyethylene resin, the organic peroxide, the monomer, the lubricant, the syndiotactic polystyrene resin, the compatilizer and the antioxidant to obtain a mixture;
processing the mixture by a double-screw extruder at 240-280 ℃ to obtain the ultra-high molecular weight polyethylene reinforced and toughened syndiotactic polystyrene composite material;
wherein the molecular weight of the ultra-high molecular weight polyethylene resin is 250-350 ten thousand;
the monomer is maleic anhydride or glycidyl acrylate;
56.4-72.6 parts by weight of syndiotactic polystyrene resin, 20-30 parts by weight of ultrahigh molecular weight polyethylene resin, 5-8 parts by weight of compatilizer, 1-2 parts by weight of antioxidant, 1-3 parts by weight of lubricant, 0.3-0.45 part by weight of organic peroxide and 0.1-0.15 part by weight of monomer;
the length-diameter ratio of the screw of the double-screw extruder is 52:1 or 56: 1.
2. The composite material according to claim 1, characterized in that it is prepared by a process comprising:
mixing an ultra-high molecular weight polyethylene resin, an organic peroxide, a monomer and a lubricant to obtain a first mixture;
mixing the syndiotactic polystyrene resin, the compatilizer and the antioxidant to obtain a second mixture;
and adding the first mixture into the double-screw extruder from a main feeding port, adding the second mixture into the double-screw extruder from a side feeding port, and processing at 240-280 ℃ to obtain the ultrahigh molecular weight polyethylene reinforced and toughened syndiotactic polystyrene composite material.
3. The composite material according to claim 1 or 2, wherein the syndiotactic polystyrene resin has a molecular weight of 8 to 12 ten thousand.
4. The preparation process of composite syndiotactic polystyrene material toughened and reinforced with superhigh molecular weight polyethylene includes the following steps:
mixing the ultra-high molecular weight polyethylene resin, the organic peroxide, the monomer, the lubricant, the syndiotactic polystyrene resin, the compatilizer and the antioxidant to obtain a mixture;
adding the mixture from a main feeding port of a double-screw extruder, and processing at 240-280 ℃ to obtain the ultra-high molecular weight polyethylene reinforced and toughened syndiotactic polystyrene composite material;
wherein the molecular weight of the ultra-high molecular weight polyethylene resin is 250-350 ten thousand;
the monomer is maleic anhydride or glycidyl acrylate;
56.4-72.6 parts by weight of syndiotactic polystyrene resin, 20-30 parts by weight of ultrahigh molecular weight polyethylene resin, 5-8 parts by weight of compatilizer, 1-2 parts by weight of antioxidant, 1-3 parts by weight of lubricant, 0.3-0.45 part by weight of organic peroxide and 0.1-0.15 part by weight of monomer;
the length-diameter ratio of the screw of the double-screw extruder is 52:1 or 56: 1.
5. The preparation method of the ultrahigh molecular weight polyethylene toughened and reinforced syndiotactic polystyrene composite material comprises the following steps:
mixing an ultra-high molecular weight polyethylene resin, an organic peroxide, a monomer and a lubricant to obtain a first mixture;
mixing the syndiotactic polystyrene resin, the compatilizer and the antioxidant to obtain a second mixture;
adding the first mixture from a main feeding port of a double-screw extruder, adding the second mixture from a side feeding port of the double-screw extruder, and processing at 240-280 ℃ to obtain the ultra-high molecular weight polyethylene reinforced and toughened syndiotactic polystyrene composite material;
wherein the molecular weight of the ultra-high molecular weight polyethylene resin is 250-350 ten thousand;
the monomer is maleic anhydride or glycidyl acrylate;
56.4-72.6 parts by weight of syndiotactic polystyrene resin, 20-30 parts by weight of ultrahigh molecular weight polyethylene resin, 5-8 parts by weight of compatilizer, 1-2 parts by weight of antioxidant, 1-3 parts by weight of lubricant, 0.3-0.45 part by weight of organic peroxide and 0.1-0.15 part by weight of monomer;
the length-diameter ratio of the screws of the twin-screw extruder is 52:1 or 56: 1.
6. The production method according to claim 4 or 5, wherein the syndiotactic polystyrene resin has a molecular weight of 8 to 12 ten thousand.
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