WO2022095364A1 - Polyester alloy composition, preparation method therefor and use thereof - Google Patents

Abstract

A polyester alloy composition, a preparation method therefor and the use thereof. The polyester alloy composition consists of polycarbonate, polyester, an acrylic shell silicone rubber, polyurethane, a toughening agent, an antioxidant and a lubricant. The polyester alloy composition has an improved gloss by adding the acrylic shell silicone rubber and polyurethane, which gives the polyester alloy composition a good matte effect, such that the requirements of various processes for the gloss can be met. In addition, the oil resistance of the polyester alloy can also be substantially improved.

Description

A kind of polyester alloy composition and its preparation method and application technical field

The invention belongs to the field of engineering plastics, and in particular relates to a polyester alloy composition and a preparation method and application thereof.

Background technique

Polyester alloy (polycarbonate and polyester) is a new type of high-performance alloy with beneficial characteristics such as high surface gloss, good toughness, and good processing fluidity. The addition of polyester can greatly improve the performance of polycarbonate. Chemical resistance, expanded to be used in various fields, especially in the fields of engineering plastics technology in electronic appliances, transportation, building materials and other fields. With the development of the industry, the requirements for the diversification of material appearance are getting higher and higher. For example, in the outdoor charging equipment shell in the new energy industry, if the shell material has a high gloss, it will cause reflection. At the same time, the high-gloss shell material is easy to fall off dust or wipe during use, resulting in appearance defects. Contact with other chemical agents requires good oil resistance (chemical resistance) stability. The matte technology of the shell material can improve the visual comfort of the material during use, and can prolong the service life of outdoor materials. Therefore, the development of matte Polyester alloys with excellent oil resistance and light effect have broad application prospects in different industries.

At present, the commonly used matte technologies are as follows:

1) Add inorganic materials, such as nano-silica, by utilizing the incompatibility and infiltration between the filler surface and the matrix resin, the filler will migrate during processing to form an uneven surface, resulting in dumb Light effect; CN201410177444.2 discloses PCABS which realizes matte effect by adding ACS and nano-silica.

2) When adding rubber with high content, especially rubber with larger particle size or a certain degree of cross-linking, the rubber and resin matrix will undergo phase separation during processing, and the micro-shrinkage of the rubber will cause the surface of the material to form a rough effect. resulting in a matte effect;

3) Adding epoxy substances, through the introduction of epoxy groups, the compatibility between ABS and PC resins is reduced, thereby reducing the gloss of the material surface, thereby producing a matte effect; CN201810442932.X has disclosed that through Add epoxy and mica powder to achieve matte finish PCABS.

4) The surface of the material can also have a certain roughness through the pattern design of the injection mold, so as to achieve a matte effect.

The above matte technology all have certain limitations. For example, the addition of fillers will lead to inconsistencies in the continuous phase of the matrix, which is likely to cause other performance defects such as mechanical properties and appearance, especially the hidden danger of weld lines during processing; a large amount of rubber and epoxy The addition will greatly affect the fluidity of the resin and reduce the rigidity of the material, so it limits the application of the material to a certain extent, especially under the thin-walled industry development trend, lower fluidity will cause greater disadvantages; Relying on the mold design is strongly dependent on the processing conditions of the material, and the applicability is not wide.

Therefore, the development of a polyester alloy composition with both matte and oil resistance has important research significance and economic value.

SUMMARY OF THE INVENTION

The purpose of the present invention is to overcome the defects or deficiencies of the prior art polyester alloy compositions of matte finish and poor oil resistance, and to provide a polyester alloy composition. Through the synergistic effect of the acrylic shell silicone rubber and the polyurethane, the invention can make the polyester alloy composition achieve a satisfactory matte effect in both injection molding and extrusion processes; in addition, the addition of the acrylic shell silicone rubber can also Provides excellent oil resistance to polyester alloy compositions.

Another object of the present invention is to provide a method for preparing the above polyester alloy composition.

Another object of the present invention is to provide the application of the above polyester alloy composition in the preparation of new energy products or electrical and electronic products.

For realizing the above-mentioned purpose of the invention, the present invention adopts following technical scheme:

A polyester alloy composition, comprising the following components by weight:

Polyester has relatively low gloss (compared to polycarbonate), polycarbonate and polyester are compounded as base resins, resulting in a resin system with relatively low gloss (compared to polycarbonate); acrylic shell Silicone rubber has good compatibility with polycarbonate (PC). The addition of acrylic shell silicone rubber with a certain particle size will partially reduce the gloss of polyester alloy and achieve a weak matte effect; polyurethane (PU) With shape memory function, it can adjust the compatibility between polycarbonate and other components, so that the rubber particles in the system shrink slightly on the surface of the composition, and it is easier to fix and form. Shell silicone rubber plays a synergistic role, giving polyester alloy a better matte effect.

The addition of polyester endows the material with excellent oil and solvent resistance, while enhancing weather resistance; the addition of transesterification inhibitors can efficiently passivate the catalytic activity of the residual catalyst in the polyester alloy and prevent the degradation of the molecules of the polyester alloy; in addition, Acrylic shell silicone rubber has better weather resistance and heat resistance; the synergy of polyester, transesterification inhibitor and acrylic shell silicone rubber can endow the polyester alloy composition with excellent oil resistance.

The polyester alloy composition provided by the invention has an injection glossiness of less than 13.5, an extrusion glossiness of less than 20.5, and excellent oil resistance, which can meet the matte effect requirements of different processing techniques (extrusion, injection molding, etc.).

Preferably, the polyester alloy composition includes the following components in parts by weight:

Polycarbonates, polyesters, tougheners, antioxidants and lubricants conventionally used in the art to prepare polyester alloy compositions can be used in the present invention.

Preferably, the weight-average molecular weight of the polycarbonate is 40,000-52,000, and the content of terminal hydroxyl groups is less than 100 ppm.

The content of terminal hydroxyl groups is measured by the following method: take a specific content of the test sample to prepare a 1% concentration (mass concentration) clear solution, rinse with neutral ethanol, add quantitative phenolphthalein indicator, and titrate with 0.5mol/L hydrochloric acid solution The content of terminal hydroxyl group is obtained according to the consumption of hydrochloric acid.

Preferably, the polyester is one or more combinations of ethylene glycol, hexylene glycol, propylene glycol, butanediol, 1.4-cyclohexanedimethanol, neopentyl glycol or terephthalimethanol, with parabenzene A copolyester obtained by polymerizing one or more combinations of dicarboxylic acid, isophthalic acid, glutaric acid, adipic acid or suberic acid, such as PBT or PET, preferably has a viscosity greater than 0.6 dl/g.

The viscosity is measured by the Ubbelohde viscometer method. Take a certain amount of polyester and add a specific volume of solvent to dissolve it completely and put it into the Ubbelohde viscometer to maintain a constant temperature of 40 °C. By measuring the flow time, and according to the solution flow time / Solvent flow time is calculated to obtain the viscosity test value of polyester.

Preferably, the silica gel content of the acrylic shell silicone rubber is greater than 10%.

Preferably, the rubber D50 of the acrylic shell silicone rubber is 800-1000 nm.

Preferably, the acrylic shell silicone rubber is one or both of S-2130 or S-2100.

Preferably, the Tg temperature of the polyurethane is lower than -30°C, the refractive index is 1.52, the oil absorption value is 50-150, and the D50 is 3-40 μm.

More preferably, the D50 of the polyurethane is 5-8 μm.

The Tg temperature of polyurethane is measured by the following method: take a specific weight of the polyurethane test sample and put it in a differential calorimeter, set the heating rate to 10 °C/min, and the heating range to -60 to 200 °C. Cycle to read the Tg temperature from the analytical curve.

The refractive index of the polyurethane was measured directly by an Abbe refractometer with a thickness of 2 mm.

The oil absorption value of the polyurethane is measured by the following method: gradually add dioctyl phthalate to the polyurethane of a fixed weight, stir well until no reagent is precipitated, and the oil absorption value of the polyurethane can be obtained according to the quality of the added reagent.

Preferably, the antioxidants are hindered phenolic antioxidants (such as 1010, 176, etc.), phosphite antioxidants (such as 168, 626, 9228, etc.) or hindered amine antioxidants (such as 1098, etc.) ) one or more of them.

Preferably, the lubricant is one or more of PETS, GTS, GMS, silicone oil or white oil.

Preferably, the transesterification inhibitor is a phosphorus-containing oxyester (such as TPP, BDP, etc.) or a phosphorus-containing metal salt derivative (such as disodium dihydrogen pyrophosphate, sodium hydrogen pyrophosphate, zinc dihydrogen phosphate, etc.) , zinc phosphate, etc.) one or more of them.

The polyester alloy composition of the present invention may also include some other functional additives to achieve more diverse properties.

For example, flame retardants (such as BDP, RDP, phenoxyphosphazene, etc., 1 to 20% by weight); antistatic agents (such as conductive carbon black, conductive graphite, polyamide polyether block copolymer, ionic liquid, etc., 1 to 30% by weight)); antibacterial agents (such as silver ion antibacterial agents with a certain carrier, etc., 0.01 to 5% by weight)); fillers (such as calcium carbonate, talc, wollastonite, titanium dioxide, sulfuric acid) barium, etc., 0.1-90% by weight)); color powder (such as inorganic pigments such as carbon black and zinc sulfide, and organic dyes such as anthraquinone, 0.001-20% by weight).

Preferably, the injection gloss of the polyester alloy composition is less than 13.5; the extrusion gloss is less than 20.5.

The polyester alloy composition provided by the present invention can be obtained by extrusion or injection molding.

Utilize extrusion process to prepare the process of obtaining polyester alloy composition as follows:

The preparation method of the above polyester alloy composition comprises the following steps: mixing polycarbonate, polyester, acrylic shell silicone rubber, polyurethane, toughening agent, antioxidant and lubricant, extruding and granulating to obtain The polyester alloy composition.

Specifically, polycarbonate, polyester, acrylic shell silicone rubber, toughening agent, antioxidant and lubricant are mixed through a high mixer and then added from the main feeding port, and the polyurethane component is separately passed through the side feeding port Adding, extruding and granulating, the polyester alloy composition is obtained.

Compared with polycarbonate, the heat resistance of the polyurethane component is poor, and adding it through the side feed port can better ensure the performance of the polyurethane.

The process of preparing the polyester alloy composition by the injection molding process is as follows:

The preparation method of the above-mentioned polyester alloy composition comprises the following steps: mixing polycarbonate, polyester, acrylic shell silicone rubber, polyurethane, toughening agent, antioxidant and lubricant, and injection molding to obtain the polyester alloy composition.

The preparation method of the invention has the advantages of simple process, strong applicability and easy popularization and application.

The application of the above polyester alloy composition in the preparation of new energy products or electrical and electronic products is also within the protection scope of the present invention.

Compared with the prior art, the present invention has the following beneficial effects:

The polyester alloy composition provided by the invention improves the gloss by adding acrylic shell silicone rubber and polyurethane, gives the polyester alloy composition a better matte effect, and can meet the requirements of various processes for gloss; , synergistic effect of transesterification inhibitor and acrylic shell silicone rubber - also enables polyester alloy composition to have excellent oil resistance.

The preparation method of the invention has the advantages of simple process, strong applicability and easy popularization and application.

Detailed ways

The present invention is further described below in conjunction with the examples. These examples are only intended to illustrate the present invention and not to limit the scope of the present invention. The experimental methods that do not specify specific conditions in the following examples are usually in accordance with the conventional conditions in the field or the conditions suggested by the manufacturer; the raw materials, reagents, etc. used, if there is no special instruction, are available from commercial channels such as conventional markets. The obtained raw materials and reagents. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of protection claimed by the present invention.

Some of the reagents selected for each embodiment of the present invention and the comparative example are described as follows:

PC resin, S-2000F, Shanghai Mitsubishi, the weight average molecular weight is 48000, and the terminal hydroxyl content is 10ppm;

PC resin, E-1000F, Shanghai Mitsubishi, the weight average molecular weight is 50000, and the terminal hydroxyl content is 25ppm;

Polyester: 1100-211 (PBT resin), Taihua Changchun, viscosity 0.85dl/g;

Polyester: BG-80 (PET resin), Yizheng Chemical, viscosity 0.80dl/g;

Polyester: FG-600 (PET resin), Yizheng Chemical, viscosity 0.6dl/g;

Acrylic shell silicone rubber: S-2130, Japan Mitsubishi Rayon, the content of silica gel is 30%, and the rubber particle size D50 is 800nm;

Acrylic shell silicone rubber: S-2100, Mitsubishi Rayon, Japan, the content of silica gel is 10%, and the rubber particle size D50 is 850nm;

Acrylic shell silicone rubber: Sx-006, Mitsubishi Rayon, Japan, the content of silica gel is 10%, and the rubber particle size D50 is 100nm;

Polyurethane: PC-8 innovative chemical industry, Tg is -48℃, refractive index is 1.52, oil absorption value is 80, D50 is 5μm;

Polyurethane: PC-5 innovative chemical industry, Tg is -35℃, refractive index is 1.52, oil absorption value is 52, D50 is 38μm;

Polyurethane: PC-3 innovative chemical industry, Tg is -35℃, refractive index is 1.52, oil absorption value is 40, D50 is 38μm;

Antioxidants: 1076 and 168, BASF;

Lubricant: PETS, hair base;

Transesterification inhibitor: disodium hydrogen pyrophosphate DHPP, Borde;

Other processing aids: toner, anthraquinone red, BASF.

The polyester alloy compositions of each example and comparative example were prepared by the following methods.

Extrusion process: Polycarbonate, polyester, acrylic shell silicone rubber, antioxidants, lubricants and transesterification inhibitors are mixed through a high mixer and then added from the main feeding port, and the polyurethane component is separately fed through the side The polyester alloy composition is obtained by adding in the feed port, extruding and granulating.

Injection molding process: mixing polycarbonate, polyester, acrylic shell silicone rubber, polyurethane, antioxidant, lubricant and transesterification inhibitor, and injection molding to obtain the polyester alloy composition.

The test methods of the various properties of the polyester alloy compositions of each embodiment of the present invention and the comparative example are as follows:

Injection Gloss: According to ASTM-D523-2014 standard, test the injection molding plate with a thickness of 3.0mm and a diameter of not less than 60mm. The injection temperature is 260°C. Use a gloss meter to test the gloss at 60°. The smaller the gloss, the better the matte effect. Well, when the injection gloss is less than 13.5° and the extrusion gloss is less than 20.5°, the comprehensive matte effect is the best.

Extrusion gloss: The sheet with a film thickness of 3.0mm is formed at an extrusion temperature of 240°C. After cooling at room temperature for 48 hours, the gloss at 60° is tested with a gloss meter according to the ASTM-D523-2014 standard. The smaller, the better the matte finish.

Oil resistance: Place the ASTM 527-2015 standard spline on a fixture with a set curvature of 1%, and apply oil of a specific brand (peanut oil, arowana) within the effective length of the spline, remove it after 24 hours, and follow the ASTM 527-2015 tests the tensile strength after oiling, and obtains the tensile strength retention rate of the oil resistance test. The higher the tensile strength retention rate, the better the oil resistance. If the tensile strength retention rate is less than 50%, the material Unusable, recorded as NG.

Examples 1 to 13

This example provides a series of polyester alloy compositions whose components are shown in Table 1.

Components (parts) of polyester alloy compositions provided in Table 1 Examples 1-13

Examples 14 to 20

This example provides a series of polyester alloy compositions whose components are shown in Table 2.

Components (parts) of polyester alloy compositions provided in Table 2 Examples 14-20

Comparative Examples 1 to 7

This comparative example provides a series of polyester alloy compositions whose components are shown in Table 3.

Components (parts) of polyester alloy compositions provided in Table 3 Comparative Examples 1-7

The properties of the polyester alloy compositions of each embodiment and comparative example were measured according to the above-mentioned test methods, and the test results are shown in Table 4.

Among them, in Comparative Example 5, because the addition amount of polyurethane was too large, extrusion/injection molding could not be performed, so the performance test could not be carried out. Comparative Example 4 developed serious cosmetic defects after extrusion/injection molding.

Table 4 Performance test results of polyester alloy compositions of each embodiment and comparative example

It can be seen from Table 4 that the polyester alloy compositions provided by the embodiments of the present invention have good oil resistance and excellent matte properties.

The addition of acrylic shell silicone rubber can make the gloss show a satisfactory matte effect. Specifically, within a certain range (Examples 1, 6-9), when the addition amount of acrylic shell silicone rubber increases, the injection molding matte effect becomes more and more obvious, and the extrusion matte effect maintains a satisfactory level; When the addition amount of silicone rubber continues to increase, the matte effect is slightly reduced due to the weakening of the synergistic effect of acrylic shell silicone rubber and polyurethane; but when the addition amount of acrylic shell silicone rubber is large, there will be hidden defects in appearance; such as Excessive addition of acrylic shell silicone rubber (such as Comparative Example 4) will cause severe delamination appearance defects in the material, and the rubber particles in the acrylic shell silicone rubber will precipitate to the surface of the composition resulting in phase separation and dullness. The light effect is only slightly improved relative to no addition (Comparative Example 1). In addition, both acrylic shell silicone rubber and polyester have good weather resistance, and transesterification inhibitors can prevent the degradation of polyester alloys. The addition of the three can improve the oil resistance of polyester alloy compositions, and with acrylic shells With the increase of the amount of silicone-like rubber added, the oil resistance is also better; while the composition without the addition of polyester with better weather resistance (such as Comparative Example 7), the oil resistance decreases, and the gloss of the base resin system is very high , the matte effect cannot be achieved by the synergy of polyurethane and acrylic shell silicone rubber.

The addition of polyurethane can improve the gloss effect. Within a certain range (Examples 1, 10-13), when the amount of polyurethane added increases, the matte effect is getting better and better, especially the extrusion matte is improved; but when the amount of polyurethane added is large, the matte effect is Due to the weakening of the synergistic effect of acrylic shell silicone rubber and polyurethane, and the reduction of the thermal stability of the system will lead to a decrease in toughness; if the amount of polyurethane added is too large (such as Comparative Example 5), it will seriously reduce the thermal stability of the system. Stability leads to the decline of toughness, and the phenomenon of inability to extrusion/injection molding occurs; when the addition amount of acrylic shell silicone rubber is 5-10, and the addition amount of polyurethane is 5-10, it has better comprehensive performance.

Since the polyester alloy composition in Comparative Example 1 is not modified, and the traditional polyester alloy composition (PCABS material) is high gloss, a matte surface texture cannot be achieved; in Comparative Example 3, only acrylic shells are added. Silicone rubber, the matte effect cannot be achieved through the addition amount; in Comparative Example 2, because only polyurethane is added, although the gloss can be reduced, it does not meet the requirements of uniform matte, and the addition of polyurethane alone will cause the polyester resin matrix to not have enough. Resilience leads to limited application. Comparative Example 6 Because the rubber particle size (D50) of the added acrylic shell silicone rubber is too small, the polyester alloy composition cannot form rubber particles with sufficient surface quality to achieve a certain diffuse reflection effect, and the effect of improving gloss is not good. .

Those of ordinary skill in the art will appreciate that the embodiments herein are intended to help readers understand the principles of the present invention, and it should be understood that the scope of protection of the present invention is not limited to such specific statements and embodiments. Those skilled in the art can make various other specific modifications and combinations without departing from the essence of the present invention according to the technical teaching disclosed in the present invention, and these modifications and combinations still fall within the protection scope of the present invention.

Claims (10)

1. A polyester alloy composition, characterized in that it comprises the following components in parts by weight:

   Polycarbonate 10 to 90 parts,

   10 to 90 parts of polyester,

   Acrylic shell silicone rubber 0.5 to 20 parts,

   Polyurethane 0.5 to 20 parts,

   Antioxidant 0.001 to 5 parts,

   Lubricant 0.001 to 5 parts,

   Transesterification inhibitor 0.001 to 5 parts,

   The rubber D50 of the acrylic shell silicone rubber is not less than 350nm.
2. The polyester alloy composition according to claim 1, characterized in that it comprises the following components in parts by weight:

   Polycarbonate 50 to 70 parts,

   30 to 50 parts of polyester,

   5-10 parts of acrylic shell silicone rubber,

   Polyurethane 5 to 10 parts,

   Antioxidant 0.01 to 2 parts,

   Lubricant 0.1 to 3 parts

   Transesterification inhibitor 0.1 to 2 parts.
3. The polyester alloy composition according to claim 1, wherein the weight average molecular weight of the polycarbonate is 40,000-52,000, and the content of terminal hydroxyl groups is not more than 100 ppm.
4. The polyester alloy composition according to claim 1, wherein the silica gel content of the acrylic shell silicone rubber is not less than 10%.
5. The polyester alloy composition according to claim 1, wherein the rubber D50 of the acrylic shell silicone rubber is 800-1000 nm.
6. The polyester alloy composition of claim 1, wherein the polyurethane has a Tg temperature of less than -30°C, a refractive index of 1.52, an oil absorption value of 50 to 150, and a D50 of 3 to 40 μm.
7. The polyester alloy composition according to claim 1, wherein the antioxidant is one or more of hindered phenol antioxidants, phosphite antioxidants or hindered amine antioxidants ; Described lubricant is one or more of PETS, GTS, GMS, silicone oil or white oil; Described transesterification inhibitor is one or more of phosphorus-containing oxyester or its metal salt derivative kind.
8. The polyester alloy composition according to claim 1, wherein the injection gloss of the polyester alloy composition is less than 13.5; the extrusion gloss is less than 20.5.
9. The method for preparing the polyester alloy composition according to any one of claims 1 to 8, characterized in that it comprises the steps of: mixing polycarbonate, polyester, acrylic shell silicone rubber, polyurethane, antioxidant, lubricant and ester The polyester alloy composition is obtained by extruding and granulating the exchange inhibitor; or mixing polycarbonate, polyester, acrylic shell silicone rubber, polyurethane, antioxidant, lubricant and transesterification inhibitor, injection molding , that is, the polyester alloy composition is obtained.
10. Application of any one of the polyester alloy compositions of claims 1 to 8 in the preparation of new energy products or electrical and electronic products.