High-melting-point high-hardness polycarbonate material and preparation method thereof

Abstract

The invention provides a high-melting-point and high-hardness polycarbonate material and a preparation method thereof, the high-melting-point and high-hardness polycarbonate material comprises the following components: polycarbonate diol, a chain extender, diisocyanate, a catalyst, a lubricant, an antioxidant, an auxiliary material and a light stabilizer, the chain extender comprises 1, 4-butanediol or 1, 4-cyclohexanedimethanol, and the catalyst comprises 1, 4-butanediol or 1, 4-cyclohexanedimethanol. Compared with an existing chain extender which mostly selects BDO and cannot meet the characteristics of high hardness and high melting point at the same time, symmetric alicyclic dihydric alcohol 1, 4-cyclohexanedimethanol is selected as a micromolecule chain extender, the chain extender is resistant to high temperature, high in deformability, high in melting point and good in transparency, and by combining control over the temperature, moisture and reaction time of the technology, the hardness and the melting point of the chain extender are greatly improved. And finally, the high-temperature-resistant polycarbonate material with high hardness and high melting point is obtained.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a high-melting-point and high-hardness polycarbonate material and a preparation method thereof. Background Art

[0002] Polycarbonate materials are a type of high-performance polymer material, mainly referring to polycarbonate diol and its derived polyurethane materials. Due to its good mechanical properties, thermal stability and heat resistance, it has a wide range of applications, and is commonly used in the construction, medical, optical, aerospace, electronics and automotive industries.

[0003] However, in the prior art, polycarbonate materials are prepared by using small molecule chain extenders for polymerization reaction. Among them, the commonly used small molecule chain extenders are usually 1.4 butanediol (BDO), with a molecular weight of 90.12 and a melting point of 20.2°C; 1,6 hexanediol (HDO), with a molecular weight of 118.7 and a melting point of 42°C; and both have a straight chain structure. The final material cannot simultaneously meet the requirements of high melting point and high hardness, which greatly limits its development in the application field.

[0004] Therefore, the related technology of high melting point and high hardness polycarbonate materials in the prior art still needs to be further improved. Summary of the invention

[0005] In view of this, the present invention proposes a high melting point and high hardness polycarbonate material and a preparation method thereof, which solves the existing technical problems.

[0006] The technical solution of the present invention is achieved in this way:

[0007] On the one hand, the present invention provides a high melting point and high hardness polycarbonate material, comprising the following components: polycarbonate diol, a chain extender, a diisocyanate, a catalyst, a lubricant, an antioxidant, an auxiliary material and a light stabilizer.

[0008] On the basis of this technical solution, it is further preferred that the chain extender includes 1,4-butanediol or 1,4-cyclohexanedimethanol.

[0009] On the basis of this technical solution, it is further preferred that the material mass percentage is 100%, including the following components:

[0010]

[0011] On the basis of this technical solution, further preferably, the molecular weight of the polycarbonate diol is 1000-3000.

[0012] On the basis of this technical solution, it is further preferred that the polycarbonate diol is selected from one of the diols having a molecular weight of 1000 to 3000, or a combination of at least two of them.

[0013] On the basis of this technical solution, further preferably, the diisocyanate includes 4,4'-diphenylmethane diisocyanate.

[0014] On the basis of this technical solution, further preferably, the catalyst is an organic bismuth catalyst.

[0015] On the basis of this technical solution, further preferably, the lubricant is montan wax ester (ie WAX-E).

[0016] On the basis of this technical solution, it is further preferred that the antioxidant includes phenolic antioxidant 1135, the light stabilizer is UV234, and the auxiliary material is 2,3,6-tri(tert-butyl)catechol (ie antioxidant 2320).

[0017] On the other hand, the present invention also provides a method for preparing the high melting point and high hardness polycarbonate material according to any one of the first aspects, comprising the following steps:

[0018] The polycarbonate diol is weighed, vacuum dehydrated at 85-95° C., a chain extender, a catalyst, a lubricant, an antioxidant, and auxiliary materials are added, and the mixture is fully mixed. Then, diisocyanate is added to react for 2-4 hours to obtain a rubber mass, which is crushed, a light stabilizer is added, the mixture is mixed, extruded, granulated, cooled, and then dried to obtain a polycarbonate material with a high melting point and high hardness.

[0019] On the basis of this technical solution, more preferably, the water content of the polycarbonate diol after vacuum dehydration is less than 0.03%.

[0020] On the basis of this technical solution, more preferably, the rubber block is crushed to a diameter of 7-9 mm.

[0021] On the basis of this technical solution, it is further preferred that the extrusion is carried out by a screw extruder, and the condition parameters include a feeding zone temperature of 175-185°C, a reaction zone temperature of 225-235°C, and an extrusion zone temperature of 205-215°C.

[0022] The high melting point and high hardness polycarbonate material and preparation method thereof provided by the present invention have the following beneficial effects compared with the prior art:

[0023] By introducing 1,4-cyclohexanedimethanol with a larger molecular weight than 1,4-butanediol during the polymerization reaction, polycarbonate materials have some properties of nylon 6, nylon 66, PC, ABS and other materials. They have outstanding advantages in application markets such as electronic wearables, electrical appliance casings, kitchen and bathroom, and high-end plastic parts: including scratch resistance, high gloss without spraying, high bending modulus, heat resistance and high toughness.

[0024] Compared with the existing chain extenders, most of which use BDO and cannot simultaneously meet the characteristics of high hardness and high melting point, symmetrical alicyclic diol 1,4-cyclohexanedimethanol (CHDM) is selected as a small molecule chain extender, which has two structures, cis and trans. The cis isomer has a melting point of 43° C., and the trans isomer has a melting point of 70° C. CHDM with a large molecular weight has the characteristics of high temperature resistance, strong deformation ability, high melting point, and good transparency. Combined with the control of temperature, moisture and reaction time by the process of the present invention, a high-hardness, high melting point and high-temperature resistant polycarbonate material is finally obtained. DETAILED DESCRIPTION

[0025] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] The present invention provides a high melting point and high hardness polycarbonate material and a preparation method thereof, which comprises the following components based on 100% by mass of the material:

[0027]

[0028] Among them, the symmetrical alicyclic diol 1,4-cyclohexanedimethanol is selected as a small molecule chain extender. The chain extender is resistant to high temperature, has strong deformation ability, high melting point and good transparency. Combined with the control of temperature, moisture and reaction time by the process of the present invention, a high-hardness, high-melting-point high-temperature resistant polycarbonate material is finally obtained.

[0029] Example 1

[0030] A high melting point and high hardness polycarbonate material comprises the following components: polycarbonate diol, chain extender, diisocyanate, catalyst, lubricant, antioxidant, auxiliary material and light stabilizer; specifically, symmetrical alicyclic diol 1,4-cyclohexanedimethanol is selected as the small molecule chain extender.

[0031] In this embodiment, specifically, the molecular weight of the polycarbonate diol is 3,000.

[0032] In this embodiment, specifically, the catalyst is an organic bismuth catalyst.

[0033] In this embodiment, specifically, the antioxidant includes phenolic antioxidant 1135, the light stabilizer is UV234, the auxiliary material is 2,3,6-tri(tert-butyl)catechol (ie, antioxidant 2320), and the lubricant is WAX-E.

[0034] More specifically, the method for preparing the high melting point and high hardness polycarbonate material comprises the following steps:

[0035] 25kg of polycarbonate diol with a molecular weight of 3000 is vacuum dehydrated at 90°C to make its moisture content less than 0.03%. The polycarbonate diol just dehydrated is fully mixed with 1g catalyst (environmentally friendly organic bismuth), 300g lubricant WAX-E, 250g primary antioxidant 1135, 50g auxiliary antioxidant 2320, 5kg 1,4-butanediol, and 18.9kg 1,4-cyclohexanedimethanol under the action of a high-speed mixer, and then 49kg of isocyanate is added and fully mixed for 2h to obtain a fixed-size rubber block, which is crushed into a semi-finished product with a diameter of 9mm by a pulverizer, and a light stabilizer UV-234500g is added to the semi-finished product, mixed evenly, and extruded by a single or twin-screw extruder.

[0036] Specifically, the extrusion parameters are set as follows: the temperature of the feeding zone is 180°C, the temperature of the reaction zone is 230°C, and the temperature of the extrusion zone is 210°C; finally, the extrusion granulation is cooled, and the granules are baked in an oven to remove moisture to obtain a high melting point and ultra-high hardness polyurethane material.

[0037] Example 2

[0038] A high melting point and high hardness polycarbonate material, which comprises the following components based on 100% by mass:

[0039]

[0040] In this embodiment, specifically, the molecular weight of the polycarbonate diol is 1000.

[0041] In this embodiment, specifically, the chain extender is 1,4-butanediol.

[0042] In this embodiment, specifically, the catalyst is an organic bismuth catalyst.

[0043] In this embodiment, specifically, the antioxidant includes phenolic antioxidant 1135, the light stabilizer is UV234, the auxiliary material is antioxidant 2320, and the lubricant is WAX-E.

[0044] In this embodiment, specifically, the diisocyanate is preferably 4,4'-diphenylmethane diisocyanate.

[0045] More specifically, the method for preparing the high melting point and high hardness polycarbonate material comprises the following steps:

[0046] The polycarbonate diol is weighed, vacuum dehydrated at 95°C, a chain extender, a catalyst, a lubricant, an antioxidant, and auxiliary materials are added, and the mixture is fully mixed. Then, diisocyanate is added to react for 4 hours to obtain a rubber mass, which is crushed, a light stabilizer is added, the mixture is mixed, extruded, granulated, cooled, and then dried to obtain a polycarbonate material with a high melting point and high hardness.

[0047] More specifically, the water content of the polycarbonate diol after vacuum dehydration is less than 0.03%.

[0048] More specifically, the gum mass is crushed to a diameter of 7 mm.

[0049] More specifically, the extrusion is carried out by a screw extruder, and the condition parameters include a feeding zone temperature of 185°C, a reaction zone temperature of 235°C, and an extrusion zone temperature of 215°C.

[0050] Example 3

[0051] A high melting point and high hardness polycarbonate material, which comprises the following components based on 100% by mass:

[0052]

[0053]

[0054] In this embodiment, specifically, the molecular weight of the polycarbonate diol is 3,000.

[0055] In this embodiment, specifically, the catalyst is an organic bismuth catalyst.

[0056] In this embodiment, specifically, the antioxidant includes phenolic antioxidant 1135, the light stabilizer is UV234, the auxiliary material is antioxidant 2320, and the lubricant is WAX-E.

[0057] More specifically, the method for preparing the high melting point and high hardness polycarbonate material comprises the following steps:

[0058] The polycarbonate diol is weighed, vacuum dehydrated at 85-95° C., a chain extender, a catalyst, a lubricant, an antioxidant, and auxiliary materials are added, and the mixture is fully mixed. Then, diisocyanate is added to react for 2 hours to obtain a rubber mass, which is crushed, a light stabilizer is added, the mixture is mixed, extruded, granulated, cooled, and then dried to obtain a polycarbonate material with a high melting point and high hardness.

[0059] Specifically, the diisocyanate is preferably 4,4'-diphenylmethane diisocyanate.

[0060] More specifically, the water content of the polycarbonate diol after vacuum dehydration is less than 0.03%.

[0061] More specifically, the gum mass is crushed to a diameter of 8 mm.

[0062] More specifically, the extrusion is carried out by a screw extruder, and the condition parameters include a feeding zone temperature of 175°C, a reaction zone temperature of 225°C, and an extrusion zone temperature of 205°C.

[0063] Example 4

[0064] A high melting point and high hardness polycarbonate material, which comprises the following components based on 100% by mass:

[0065]

[0066] In this embodiment, specifically, the molecular weight of the polycarbonate diol is 3,000.

[0067] In this embodiment, specifically, the catalyst is an organic bismuth catalyst.

[0068] In this embodiment, specifically, the antioxidant includes phenolic antioxidant 1135, the light stabilizer is UV234, the auxiliary material is antioxidant 2320, and the lubricant is WAX-E.

[0069] More specifically, the method for preparing the high melting point and high hardness polycarbonate material comprises the following steps:

[0070] The polycarbonate diol is weighed, vacuum dehydrated at 85°C, a chain extender, a catalyst, a lubricant, an antioxidant, and auxiliary materials are added, and the mixture is fully mixed. Then, diisocyanate is added to react for 3 hours to obtain a rubber mass, which is crushed, a light stabilizer is added, the mixture is mixed, extruded, granulated, cooled, and then dried to obtain a polycarbonate material with a high melting point and high hardness.

[0071] More specifically, the water content of the polycarbonate diol after vacuum dehydration is less than 0.03%.

[0072] More specifically, the gum mass is crushed to a diameter of 7 mm.

[0073] More specifically, the extrusion is carried out by a screw extruder, and the condition parameters include a feeding zone temperature of 185°C, a reaction zone temperature of 235°C, and an extrusion zone temperature of 215°C.

[0074] Example 5

[0075] A high melting point and high hardness polycarbonate material comprises the following components: polycarbonate diol, chain extender, diisocyanate, catalyst, lubricant, antioxidant, auxiliary material and light stabilizer; specifically, symmetrical alicyclic diol 1,4-cyclohexanedimethanol is selected as the small molecule chain extender.

[0076] In this embodiment, specifically, the polycarbonate diols are PCDL2000 and PCDL3000.

[0077] The preparation method of the high melting point and high hardness polycarbonate material comprises the following steps:

[0078] 12kg of polycarbonate diol with a molecular weight of 2000 and 12kg of polycarbonate diol with a molecular weight of 3000 were vacuum dehydrated at 90°C to make the moisture content less than 0.03%. The polycarbonate diol just dehydrated was fully mixed with 1g of catalyst (environmentally friendly organic bismuth), 300g of lubricant WAX-E, 250g of primary antioxidant 1135, 50g of auxiliary antioxidant 2320, 5kg of 1,4-butanediol, and 18.6kg of 1,4-cyclohexanedimethanol under the action of a high-speed mixer, and then 48.6kg of isocyanate was added and fully mixed for 2h to obtain a fixed-size rubber block, which was crushed into a semi-finished product with a diameter of 9mm by a pulverizer, and 500g of light stabilizer UV-234 was added to the semi-finished product and mixed evenly, and then extruded by a single or twin-screw extruder.

[0079] Specifically, the extrusion parameters are set as follows: the temperature of the feeding zone is 180°C, the temperature of the reaction zone is 230°C, and the temperature of the extrusion zone is 210°C; finally, the extrusion granulation is cooled, and the granules are baked in an oven to remove moisture to obtain a high melting point and ultra-high hardness polyurethane material.

[0080] Performance Testing

[0081] The high melting point and high hardness polycarbonate material obtained in Example 1 was subjected to tests related to hardness, mechanical strength, melting point, etc., and the same test was performed on nylon 66.

[0082] Table 1 Performance test

[0083] Performance Project Nylon 66 Example 1 Hardness (Shore D) 80 82 <![CDATA[Specific gravity (g / cm 3 )]]> 1.280 1.200 Tensile strength(MPa) 78 58 Elongation(%) 3.5 12 Bending strength(MPa) 113 81 Flexural modulus (MPa) 1300 2200 <![CDATA[Notched impact strength (KJ / m 2 )]]> 7 13 Melting point(℃) 267 355

[0084] From the above results, it can be seen that the polycarbonate material obtained in Example 1 is inferior to nylon 66 in tensile strength, flexural strength and flexural modulus, but its hardness, notched impact strength and elongation are better than nylon 66, and it also has a higher melting point. It can be seen that the polycarbonate material obtained by the method of this embodiment has the following characteristics:

[0085] High gloss spray-free: The surface gloss of injection molded products is high, which can replace the materials that need surface spraying to save costs and reduce environmental pollution;

[0086] High flexural modulus: The flexural modulus of the manufactured products can reach more than 2200MPa, which can provide better elasticity and torsion resistance to ensure the accuracy and reliability of the equipment;

[0087] Heat resistance: The melting point of this material is about 350℃ as measured by DSC. It can maintain its physical properties and structural integrity at higher temperatures, making it very suitable for the production of parts that need to work in high temperature environments;

[0088] High toughness: According to the test of nylon 66 and TPBC at 25°C, the elongation at break of the latter is more than 3 times that of the former, so compared with the two, TPBC has higher toughness.

[0089] In summary, the present invention provides a high melting point and high hardness polycarbonate material and a preparation method thereof, which uses polycarbonate (TPBC) material to replace other plastic resins, which can increase the flexibility of product design, bring more application effects and experiences, and reduce some processing steps.

[0090] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A high melting point and high hardness polycarbonate material, characterized in that: The invention comprises the following ingredients: polycarbonate diol, chain extender, diisocyanate, catalyst, lubricant, antioxidant, auxiliary material and light stabilizer.

2. The high melting point and high hardness polycarbonate material according to claim 1, characterized in that: The chain extender includes 1,4-butanediol or 1,4-cyclohexanedimethanol.

3. The high melting point and high hardness polycarbonate material according to claim 2, characterized in that: Taking the material mass percentage as 100%, it includes the following components:

4. The high melting point and high hardness polycarbonate material according to claim 2, characterized in that: The molecular weight of the polycarbonate diol is 1000-3000.

5. The high melting point and high hardness polycarbonate material according to claim 2, characterized in that: The catalyst is an organic bismuth catalyst.

6. The high melting point and high hardness polycarbonate material according to claim 2, characterized in that: The antioxidant comprises phenolic antioxidant 1135, the light stabilizer is UV234, the auxiliary material is 2,3,6-tri(tert-butyl)catechol, and the lubricant is montan wax ester.

7. The method for preparing a high melting point and high hardness polycarbonate material according to any one of claims 1 to 6, characterized in that: The following steps are involved: The polycarbonate diol is weighed, vacuum dehydrated at 85-95° C., a chain extender, a catalyst, a lubricant, an antioxidant, and auxiliary materials are added, and the mixture is fully mixed. Then, diisocyanate is added to react for 2-4 hours to obtain a rubber mass, which is crushed, a light stabilizer is added, the mixture is mixed, extruded, granulated, cooled, and then dried to obtain a polycarbonate material with a high melting point and high hardness.

8. The method for preparing the high melting point and high hardness polycarbonate material according to claim 7, characterized in that: The water content of the polycarbonate diol after vacuum dehydration is less than 0.03%.

9. The method for preparing the high melting point and high hardness polycarbonate material according to claim 7, characterized in that: The rubber block is crushed to a diameter of 7-9 mm.

10. The method for preparing the high melting point and high hardness polycarbonate material according to claim 7, characterized in that: The extrusion is carried out by a screw extruder, and the condition parameters include a feeding zone temperature of 175-185°C, a reaction zone temperature of 225-235°C, and an extrusion zone temperature of 205-215°C.

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