Polymer mixed composition

Abstract

The present invention provides a polymer blend composition, the polymer blend composition comprising: a polycarbonate compound; an organosilicon compound; a polyterephthalic acid cyclohexane compound; and a copolymerized compound of dimethyl terephthalate, cyclohexanedimethanol, and 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol. The composition comprises a polycarbonate compound, an organosilicon compound, a polyterephthalic acid cyclohexane compound, and a copolymerization compound of dimethyl terephthalate, cyclohexanedimethanol, and 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol, therefore, transparency can be ensured even if the organic silicon compound is included, and durability and heat resistance can be improved.

Description

Technical Field

[0001] The present invention relates to a polymer mixed composition, and more particularly, to a polymer mixed composition which is transparent even if it contains silicone. Background Art

[0002] Plastic refers to a solid that is artificially made into a useful shape using polymer as the main raw material. Specifically, it is a material that melts and has fluidity when heated or pressurized.

[0003] This type of plastic can be used to make light and strong products. It will not rust or decay in acids and alkalis, has excellent insulation and heat insulation properties, can be colored freely, is easy to mass produce and process, and has low processing costs. Therefore, it is widely used in the manufacture of automotive parts, white appliance parts, office equipment parts, building materials, daily necessities or various other products.

[0004] Representative materials of this type of plastic include polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile butadiene styrene (ABS resin), polyethylene terephthalate (PET), polyacetal (Polyacetal), polyamide (PA6.66, Polyamide, nylon) and other polymers.

[0005] A typical example of such plastic materials is polycarbonate resin, which has high flame resistance and transparent properties. However, this resin contains a large amount of compounds harmful to the human body, such as bisphenol A, and is therefore not suitable as an environmentally friendly resin.

[0006] Among the raw materials of this plastic, the copolyester called polycyclohexylenedimethyleneterephtalate glycol (PCTG) did not contain any bisphenol A and has attracted much attention as an environmentally friendly material.

[0007] The patent documents shown below can be used as examples of plastic compositions or products containing such polycyclohexyl terephthalate.

[0008] Here, the following patent documents containing plastic compositions or products are reviewed, which contain existing polycyclohexyl terephthalate. When only the above polycyclohexyl terephthalate is used for manufacturing, although it is easy to mold, after molding, there is a disadvantage that the strength and heat resistance of the finished product are relatively lower than those of other plastics.

[0009] Organic silicon substances have been proposed as substances for solving such problems. However, when applied to existing polymers, there is a problem that the prepared plastics are not transparent and their applications as products are limited, and thus technical development is still required.

[0010] Prior art literature

[0011] Patent Literature

[0012] Korean Patent Publication No. 10-2017-0100945

[0013] Korean Patent No. 10-1004614 Summary of the invention

[0014] Technical issues

[0015] Therefore, in view of the above circumstances, the present invention aims to solve the various disadvantages and problems caused by the prior art, and its object is to provide a polymer mixed composition that can improve heat resistance and durability and maintain transparency by using silicone.

[0016] Solutions to the problem

[0017] In order to achieve the above-mentioned purpose, according to one embodiment of the present invention, the present invention provides a polymer mixed composition, comprising: a polycarbonate (PC) compound; an organosilicon compound; a polycyclohexane terephthalate compound; and a copolymer compound of dimethyl terephthalate (DMT), cyclohexanedimethanol (CHDM) and 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD).

[0018] According to an embodiment of the present invention, the content of the organic silicon compound may be less than 10 parts by weight relative to 100 parts by weight of the total weight.

[0019] According to an embodiment of the present invention, the polycarbonate compound may be as shown in the following Chemical Formula 1.

[0020] Chemical formula 1:

[0021]

[0022] According to an embodiment of the present invention, the organosilicon compound may be as shown in the following Chemical Formula 2.

[0023] Chemical formula 2:

[0024]

[0025] According to an embodiment of the present invention, the polycyclohexane terephthalate compound may be as shown in the following chemical formula 3.

[0026] Chemical formula 3:

[0027]

[0028] Among them, 0 <x≤10 3 , 0 <y≤10 3 .

[0029] The weight average molecular weight of the polymer mixed composition according to an embodiment of the present invention may be 20,000 to 30,000.

[0030] The IV value of the polymer mixed composition according to an embodiment of the present invention may be 0.5 to 0.6.

[0031] According to an embodiment of the present invention, the polyethylene terephthalate compound may be obtained by copolymerizing polyethylene terephthalate resin and cyclohexanedimethanol.

[0032] According to an embodiment of the present invention, the polycyclohexane terephthalate compound may include a first polycyclohexane terephthalate and a second polycyclohexane terephthalate. The first polycyclohexane terephthalate and the second polycyclohexane terephthalate may be prepared by copolymerizing cyclohexanedimethanol added to polyethylene terephthalate resin in different proportions.

[0033] According to an embodiment of the present invention, the heat resistance of the first polyethylene cyclohexyl terephthalate may be relatively lower than the heat resistance of the second polyethylene cyclohexyl terephthalate.

[0034] According to an embodiment of the present invention, the polycyclohexane terephthalate compound may further include polycarbonate.

[0035] According to one embodiment of the present invention, relative to 100 parts by weight of the above-mentioned polycyclohexyl terephthalate compound, the content of the above-mentioned first polycyclohexyl terephthalate may be 65 parts by weight to 75 parts by weight, the content of the above-mentioned second polycyclohexyl terephthalate may be 5 parts by weight to 15 parts by weight, and the content of the above-mentioned polycarbonate may be 10 to 30 parts by weight.

[0036] Effects of the Invention

[0037] According to the polymer mixed composition of the present invention, the above-mentioned composition contains a polycarbonate compound, an organosilicon compound, a polycyclohexane terephthalate compound, and a copolymer compound of dimethyl terephthalate, cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, so that it has the advantages of ensuring transparency and improving durability and heat resistance even if it contains an organosilicon compound.

[0038] The effects of the present invention are not limited to the above effects, and those skilled in the art can clearly understand other effects not mentioned through the following description. DETAILED DESCRIPTION

[0039] Hereinafter, the present invention will be described in detail. Prior to this, the terms or words used in this specification and the scope of the patent claims should not be interpreted as being limited to the usual or dictionary meanings, and should be interpreted as being consistent with the meaning and concept of the technical idea of ​​the present invention based on the principle that the inventor can appropriately define the concept of the term to explain his own invention in the best way. Therefore, the composition described in the embodiment described in this specification is only a most preferred embodiment of the present invention, and does not represent all the technical ideas of the present invention, so it should be understood that various equivalents and modifications that can replace these may exist when submitting this application.

[0040] The polymer mixed composition according to an embodiment of the present invention includes a polycarbonate compound, an organosilicon compound, a polycyclohexane terephthalate compound, and a copolymer compound of dimethyl terephthalate, cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0041] In the present invention, polycarbonate is a resin polymerized from carbonates, a colorless, transparent, amorphous thermoplastic polymer composed of a chain structure of bisphenol A (BPA) and phosgene, and also a type of engineering plastic. The bonds between the monomer units are composed of carbonates, i.e., carbonates (-O-(C=O)-O-), which are easy to process and can be injection molded and thermoformed. Polycarbonate used for engineering is a hard and rough material, and some grades are optically transparent. Due to this property, polycarbonate can be widely used as a material for various products in many application fields in the modern chemical industry.

[0042] In addition, since polycarbonate has excellent heat resistance, impact resistance and transparency, it can be used as commodity plastics, engineering plastics and reinforced plastics to replace glass. It is a highly functional plastic that is widely used as a raw material for media optical storage media materials such as CDs and DVDs, including exterior finishing materials for IT products such as mobile phones, laptops and monitors.

[0043] The polycarbonate that can be applied to the present invention can be used without restriction as long as it is prepared by the synthesis method used in the present technical field. As a non-limiting example, bisphenol A and phosgene (or diphenyl carbonate) can be used as raw materials for production, and in the case of using carbonyl chloride (phosgene), it can be polymerized by interfacial polycondensation, or in the case of using diphenyl carbonate, it can be synthesized by polymerization caused by ester exchange.

[0044] On the other hand, the present inventors have confirmed that when the polycarbonate shown in the following Chemical Formula 1 is used, it interacts with the organic silicon compound, the polycyclohexane terephthalate compound, and the copolymer compound of dimethyl terephthalate, cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol used together, so that durability, heat resistance and transparency are excellent.

[0045] Chemical formula 1:

[0046]

[0047] In the present invention, silicone refers to a polymer with a silicon-oxygen bond (...-Si-O-Si-O-...) as the main axis. As a non-limiting example, it may refer to a siloxane bond (...-Si-O-Si-O-...) formed by hydrolysis of dichlorodimethylsilane synthesized by reacting crystalline silicone with methyl chloride (CH3Cl), and may be composed of linear polydimethylsiloxane and oligosiloxane molecules.

[0048] In this case, according to a preferred embodiment, the above-mentioned organosilicon compound can be a compound as shown in the following Chemical Formula 2, and it is confirmed that when the organosilicon compound as shown in the following Chemical Formula 2 is used, it interacts with the polycarbonate, polycyclohexane terephthalate compound, and copolymer compound of dimethyl terephthalate, cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol used together, so that durability, heat resistance and transparency are excellent.

[0049] Chemical formula 2:

[0050]

[0051] Meanwhile, according to one embodiment of the present invention, the content of the above-mentioned organosilicon compound may be 10 parts by weight or less, preferably 5 parts by weight to 10 parts by weight, relative to 100 parts by weight of the total weight of the polymer mixed composition. When the above-mentioned range is exceeded, there is a problem that the physical properties of durability, heat resistance and transparency to be achieved by the present invention cannot be achieved at the same time.

[0052] In the present invention, the polycyclohexane terephthalate compound may be obtained by copolymerizing polyethylene terephthalate resin and cyclohexanedimethanol. According to a preferred embodiment, the polycyclohexane terephthalate compound shown in the following chemical formula 3 may be used.

[0053] Chemical formula 3:

[0054]

[0055] Among them, 0 <x≤10 3 , 0 <y≤10 3 .

[0056] Furthermore, according to a preferred embodiment of the present invention, the polycyclohexyl terephthalate compound may include a first polycyclohexyl terephthalate, a second polycyclohexyl terephthalate and a polycarbonate resin.

[0057] The first polycyclohexyl terephthalate is obtained by copolymerizing cyclohexanedimethanol by adding cyclohexanedimethanol to polyethylene terephthalate resin. Specifically, in a crystalline copolymer formed by the reaction of terephthalic acid and ethylene glycol, a part of the ethylene glycol is replaced by 1,4-cyclohexanedimethanol. The first polycyclohexyl terephthalate has the advantages of not generating bisphenol A, not generating harmful substances when incinerated or discarded, and having high transparency due to a relatively lower crystallinity than other polycyclohexyl terephthalate resins. However, the heat resistance of the first polycyclohexyl terephthalate is relatively lower than that of other plastic raw materials, and can only be used at a temperature of about 70°C, so the hot contents must be cooled before being placed in a container, and cannot be used in automatic dishwashers or microwave ovens.

[0058] The second polyethylene terephthalate is obtained by copolymerizing polyethylene terephthalate resin with cyclohexanedimethanol. Specifically, in a non-crystalline copolymer formed by the reaction of terephthalic acid and ethylene glycol, a portion of the ethylene glycol is replaced by the cyclohexanedimethanol. The second polyethylene terephthalate is added with the cyclohexanedimethanol at a different ratio from that of the first polyethylene terephthalate.

[0059] The second polyethylene cyclohexyl terephthalate has a characteristic of having relatively higher durability than the first polyethylene cyclohexyl terephthalate, and thus functions as a reinforcing material to improve the durability of the first polyethylene cyclohexyl terephthalate.

[0060] As the amount of the second polycyclohexyl terephthalate added to the polymer blend composition increases, the impact strength increases in proportion to the amount.

[0061] The first polycyclohexyl terephthalate, the second polycyclohexyl terephthalate and the polycarbonate resin are provided in the form of solid polymer pellets.

[0062] Here, when the first polycyclohexyl terephthalate, the second polycyclohexyl terephthalate and the polycarbonate resin are respectively made into pellets, the polymers respectively composed are hybridized or mixed for production. In this case, moisture is contained in the production process, which is called initial moisture content, and the initial moisture content is generally 0.3 to 5%.

[0063] In the past, in the injection molded product prepared from the above polymer mixed composition, there was a problem of subsequent generation of gas due to the above moisture, and before starting the molding of the above injection molded product, when the purge work was performed at an appropriate temperature for molding, there was a problem of hindering the above purge work due to the generation of liquid or bubbles. Due to these problems, it is difficult to normally perform the molding work of the above injection molded product. Therefore, in order to solve the above problems, the dehumidification process described later must be performed in this embodiment.

[0064] The dehumidification process is a process for reducing the initial water content by removing the water contained in each of the first polycyclohexyl terephthalate, the second polycyclohexyl terephthalate and the polycarbonate resin before mixing the first polycyclohexyl terephthalate, the second polycyclohexyl terephthalate and the polycarbonate resin to prepare the polymer mixed composition. Specifically, the water inside and outside the polymers (the first polycyclohexyl terephthalate, the second polycyclohexyl terephthalate and the polycarbonate resin) in the form of particles is evaporated by electromagnetic wave energy. For example, a microwave oven that converts electromagnetic wave energy into heat can be used to evaporate the water inside the polymer. Preferably, the dehumidification process is performed for 3 to 5 hours to reduce the water content of each polymer to less than 0.03%.

[0065] The first polycyclohexyl terephthalate, the second polycyclohexyl terephthalate or the polycarbonate resin which has been subjected to the dehumidification process are provided in the form of aluminum packaging to prevent external moisture from penetrating. Then, when the injection molded article is prepared by using the polymer mixed composition made of the first polycyclohexyl terephthalate, the second polycyclohexyl terephthalate and the polycarbonate resin which have been subjected to the dehumidification process, high-quality injection molded articles can be prepared, and the molding of the injection molded articles which has been a problem in the past can be freely performed.

[0066] In this embodiment, only two polycyclohexyl terephthalate compounds such as the first polycyclohexyl terephthalate and the second polycyclohexyl terephthalate are provided, but this is only exemplary, and of course, other polycyclohexyl terephthalate compounds may be included. In addition, at least one of the multiple polycyclohexyl terephthalate compounds may be mixed with an additional substance to improve strength and durability.

[0067] The polycarbonate resin is a type of thermoplastic plastic and has excellent impact resistance, heat resistance, weather resistance, self-extinguishing property, transparency, impact strength of about 150 times that of tempered glass, and excellent flexibility and processability. Due to the above advantages, the low heat resistance of the first polycyclohexyl terephthalate and the second polycyclohexyl terephthalate can be improved.

[0068] Relative to 100 parts by weight of the polycyclohexyl terephthalate compound, the content of the first polycyclohexyl terephthalate is 65 parts by weight to 75 parts by weight, the content of the second polycyclohexyl terephthalate is 5 parts by weight to 15 parts by weight, and the content of the polycarbonate resin is 10 parts by weight to 30 parts by weight. Preferably, relative to 100 parts by weight of the polymer mixed composition, the content of the first polycyclohexyl terephthalate is 65 parts by weight, the content of the second polycyclohexyl terephthalate is 10 parts by weight, and the content of the polycarbonate resin is 25 parts by weight.

[0069] If the content of the second polycyclohexyl terephthalate is less than 5 parts by weight relative to 100 parts by weight of the polycyclohexyl terephthalate compound, the impact strength is significantly reduced. On the contrary, if the content is greater than 15 parts by weight, the impact strength is improved, but a large amount of residual monomers are generated during injection molding of the polymer mixed composition, which causes the residual monomers to adhere to the injection molded product. Therefore, preferably, the content of the second polycyclohexyl terephthalate is 5 to 15 parts by weight.

[0070] Furthermore, when the content of the polycarbonate resin is less than 10 parts by weight relative to 100 parts by weight of the polycyclohexyl terephthalate compound, the amount of bisphenol A detected is significantly reduced, but there is a problem of very weak heat resistance, and conversely, when the content is greater than 30 parts by weight, the heat resistance becomes excellent, but there is a problem of increased value of bisphenol A. Therefore, preferably, the content of the polycarbonate resin is 10 to 30 parts by weight.

[0071] The polycyclohexyl terephthalate compound having the above-mentioned composition is prepared by melt-mixing the first polycyclohexyl terephthalate, the second polycyclohexyl terephthalate, and the polycarbonate resin in a composite form.

[0072] In the present invention, a copolymer compound of dimethyl terephthalate, cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol may be mixed.

[0073] In this case, the above-mentioned dimethyl terephthalate, cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol monomers can be copolymerized in a ratio of 1:1:1 to 1:1:3, preferably, in a ratio of 1:1:2. When the above-mentioned range is met, it has the advantage of not producing ash or only producing a slight degree of ash while maintaining the advantages of the silicone used together.

[0074] In this case, the dimethyl terephthalate is a compound represented by the following Chemical Formula 4, and a compound formed from terephthalic acid and methanol can be used.

[0075] Chemical formula 4:

[0076]

[0077] On the other hand, the cyclohexanedimethanol is a compound represented by the following chemical formula 5, and can be used to produce polyester resin.

[0078] Chemical formula 5:

[0079]

[0080] Next, the above-mentioned 2,2,4,4-tetramethyl-1,3-cyclobutanediol may be a compound represented by the following Chemical Formula 6.

[0081] Chemical formula 6:

[0082]

[0083] The above-mentioned injection-molded products obtained by injection molding the polymer mixed composition of one embodiment of the present invention may include, for example, water bottles, eyeglass frames, and automobile parts. Compared with the existing products prepared only with polyethylene cyclohexane terephthalate, they have the characteristics of long life, high strength, thermal stability, and easy color presentation while being transparent.

[0084] Hereinafter, the polymer mixed composition will be described with reference to experimental data based on the respective constituent ratios of the polymers contained in the polymer mixed composition as the background.

[0085] Table 1

[0086] Experimental data based on the composition ratios of the polymers constituting the polymer blend composition

[0087]

[0088]

[0089] Copolymer compound 1 in Table 1 is a copolymer obtained by polycondensing dimethyl terephthalate: cyclohexanedimethanol: 2,2,4,4-tetramethyl-1,3-cyclobutanediol at a molar ratio of 1:1:1. On the other hand, copolymer compound 2 is a copolymer obtained by polycondensing dimethyl terephthalate: cyclohexanedimethanol: 2,2,4,4-tetramethyl-1,3-cyclobutanediol at a molar ratio of 1:1:2.

[0090] As can be seen from the test in Table 1, it can be confirmed that the polymer mixed composition mixed in the ratio according to one embodiment of the present invention still has no smoke or only fine smoke even if it contains silicone.

[0091] Table 2

[0092] Environmentally friendly polyester testing of polymer blend compositions

[0093]

[0094] On the other hand, Table 2 shows the test results of the environmentally friendly polyester of copolymer compound 1, copolymer compound 2, and test 3 and test 4, and it can be confirmed that the glass transition temperature of the polymer mixed composition of one embodiment of the present invention is 112°C and 115°C, showing a glass transition temperature suitable for resin. It can be confirmed that the IV value and molecular weight are also similar to those of the existing copolymer compound used alone, so transparency can still be maintained even if silicone is included.

[0095] As described above, although the present invention is described by limited embodiments, the present invention is not limited to the above embodiments, and a person skilled in the art to which the present invention belongs can make various modifications and variations from such descriptions.

Claims

1. A polymer mixed composition, characterized in that: Include: Polycarbonate compounds; Silicone compounds; Polycyclohexane terephthalate compounds; and A copolymer of dimethyl terephthalate, cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

2. The polymer blend composition according to claim 1, characterized in that: The content of the organic silicon compound is 10 parts by weight or less relative to 100 parts by weight of the total weight.

3. The polymer mixed composition according to claim 1, characterized in that: The polycarbonate compound is shown in the following chemical formula 1:

4. The polymer blend composition according to claim 1, characterized in that: The organosilicon compound is shown in the following chemical formula 2:

5. The polymer blend composition according to claim 1, characterized in that: The polycyclohexane terephthalate compound is shown in the following chemical formula 3: Among them, 0 <x≤10 3 , 0 <y≤10 3 .

6. The polymer blend composition according to claim 1, characterized in that: The weight average molecular weight is 20,000 to 30,000.

7. The polymer blend composition according to claim 1, characterized in that: The IV value is 0.5 to 0.

6.

8. The polymer blend composition according to claim 1, characterized in that: The polyethylene cyclohexane terephthalate compound is prepared by copolymerization of polyethylene terephthalate resin and cyclohexanedimethanol.

9. The polymer blend composition according to claim 1, characterized in that: The polycyclohexyl terephthalate compound comprises a first polycyclohexyl terephthalate and a second polycyclohexyl terephthalate, wherein the first polycyclohexyl terephthalate and the second polycyclohexyl terephthalate are obtained by copolymerizing cyclohexanedimethanol added to polyethylene terephthalate resin in different proportions.

10. The polymer mixed composition according to claim 9, characterized in that: The heat resistance of the first polycyclohexyl terephthalate is relatively lower than the heat resistance of the second polycyclohexyl terephthalate.

11. The polymer blend composition according to claim 9, characterized in that: The polycyclohexane terephthalate compound also includes polycarbonate.

12. The polymer blend composition according to claim 11, characterized in that: With respect to 100 parts by weight of the polycyclohexyl terephthalate compound, the content of the first polycyclohexyl terephthalate is 65 parts by weight to 75 parts by weight, the content of the second polycyclohexyl terephthalate is 5 parts by weight to 15 parts by weight, and the content of the polycarbonate is 10 parts by weight to 30 parts by weight.

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