A transparent thermoplastic elastomer composition with controllable hardness and preparation and application thereof

Abstract

The present application belongs to the technical field of polymer, and particularly relates to a transparent thermoplastic elastomer composition with controllable hardness, comprising polymer A and polymer B; the polymer A is SEBS, wherein the EB segment is a hydrogenated diene polymer segment with a random structure and / or a 1,2 structure content greater than or equal to 60%; the polymer B is a polymer with full hydrogenation of aryl and olefin groups in SBS. The present application also includes preparation and application of the composition. The composition can achieve high light transmittance, low haze and controllable hardness effect.

Description

Technical Field

[0001] This invention belongs to the field of styrene-based thermoplastic elastomers, specifically a high-transparency, high-flow thermoplastic elastomer composition with adjustable hardness and its preparation method. Technical Background

[0002] SBS is a linear triblock copolymer with polystyrene as the end segment and polybutadiene as the middle elastic block. SEBS is a linear triblock copolymer with polystyrene as the end segment and ethylene-butene copolymer (obtained by hydrogenation of polybutadiene) as the middle elastic block. Its main characteristics are: at room temperature, the ethylene / butene (EB) elastomer block in the middle of SEBS is a soft block, while the two polystyrene (PS) segments on both sides are hard plastic blocks. The two blocks are thermodynamically incompatible with each other. When they are combined, they form a two-phase structure, exhibiting a microscopic phase separation state, which greatly affects its light transmittance and haze.

[0003] To address this issue, the industry has offered several solutions. For example, patent CN101747578A discloses a high-flow-rate TPE and its preparation method, wherein the TPE is prepared from polypropylene, compatibilizer, SEBS, white oil, α-methylstyrene, and antioxidant. Another example is patent CN114276643A, which discloses a highly transparent, highly resilient, and smooth thermoplastic elastomer material, comprising the following components by mass percentage: 94.5-99.9% highly transparent, highly resilient thermoplastic elastomer material, 0.1-5.5% smoothing agent; the highly transparent, highly resilient thermoplastic elastomer material includes a high-vinyl-content hydrogenated styrene thermoplastic elastomer, filler oil, a second elastomer, polypropylene, and additives. While existing technologies claim to achieve good transparency, light transmittance still needs improvement. Furthermore, the compositions in existing technologies exhibit poor haze performance and struggle to achieve good hardness control. For example, the composition described in CN114276643 A has a maximum light transmittance of only 89% and a minimum haze of 45.4%. In summary, the industry urgently needs transparent compositions that balance high light transmittance, low haze, and controllable hardness. Summary of the Invention

[0004] To address the problem that existing polymer compositions struggle to balance transparency, haze, and hardness, the primary objective of this invention is to provide a transparent thermoplastic elastomer composition with controllable hardness. This aims to offer a novel resin composition that combines excellent light transmittance with low haze and controllable hardness.

[0005] A second objective of this invention is to provide the preparation and application of the aforementioned transparent thermoplastic elastomer composition.

[0006] Existing transparent resin compositions struggle to simultaneously achieve high light transmittance and low haze, and also find it difficult to meet hardness requirements. To address this issue, the present invention provides the following solution:

[0007] A transparent thermoplastic elastomer composition with controllable hardness, comprising polymer A and polymer B;

[0008] The polymer A is SEBS, wherein the EB segment is a hydrogenated diene polymer segment with a random and / or 1,2 structure content greater than or equal to 60%.

[0009] The polymer B is a fully hydrogenated polymer of aryl and olefinic groups in SBS.

[0010] This invention innovatively discovers that by combining polymer A with random EB and / or EB shorts containing 1,2 structure content greater than or equal to 60% and fully hydrogenated polymer B, a synergistic effect can be achieved, resulting in a resin composition with high transparency, low haze, and controllable hardness.

[0011] In this invention, the structure of polymer A and polymer B and their combined use are key to synergistically improving light transmittance, reducing haze, and achieving controllable hardness.

[0012] Preferably, polymer A is at least one of Baling Petrochemical's YH-505 and YH-530; more preferably, it is YH-530. Preferably, polymer B is at least one of Formosa Plastics Corporation's CBC0510 and CBC1325X. This invention has found that innovatively combining preferred grades of polymer A and polymer B can achieve a better synergistic effect, further enabling the composition to balance high light transmittance, low haze, and good hardness.

[0013] In this invention, in the transparent thermoplastic elastomer composition with controllable hardness, polymer A comprises 1 to 99 parts by weight, and polymer B comprises 1 to 99 parts by weight. Preferably, polymer A comprises 20 to 80 parts by weight, and polymer B comprises 20 to 80 parts by weight.

[0014] Preferably, the transparent thermoplastic elastomer composition with controllable hardness also contains plasticizing oil. This invention has found that, with the combined synergistic effect of polymers A and B, further addition of plasticizing oil can further improve the synergistic effect of polymers A and B, and can further improve the light transmittance, reduce haze, and improve hardness control performance of the composition while reducing the amount of polymer used.

[0015] Preferably, the plasticizing oil is white oil; more preferably, it is hydrogenated white oil, and more preferably, it is 26# white oil. This invention has found that using the preferred hydrogenated white oil, especially 26# white oil, can further enhance the synergistic effect of polymers A and B, and further improve the balance of transmittance, haze, and hardness of the composition.

[0016] Preferably, the plasticizer oil has a weight of less than or equal to 50 parts; more preferably, it has a weight of 20 to 40 parts.

[0017] Preferably, it also includes an antioxidant. The antioxidant can be an antioxidant known in the industry, for example, it can be a combination of a phenolic antioxidant and a phosphite antioxidant, or more specifically, it can be a combination of antioxidant 1010 and antioxidant 168.

[0018] Preferably, the antioxidant is less than or equal to 1 part by weight;

[0019] Preferably, the antioxidant is present in an amount of 0.1 to 0.5 parts by weight.

[0020] The preferred transparent thermoplastic elastomer composition with controllable hardness of the present invention comprises polymer A, polymer B, white oil, and antioxidant.

[0021] Wherein, polymer A is at least one of YH-505 and YH-530;

[0022] The polymer B is at least one of CBC0510 and CBC1325X.

[0023] Furthermore, in the composite material A of polymer A, polymer B, and white oil, the weight percentage of polymer A is 20-80 wt.%; the weight percentage of polymer B is 20-80 wt.%; the content of white oil is less than or equal to 40 wt.%; and the weight percentage of antioxidant in composite material A is 0.1-0.5 wt%.

[0024] Further preferably, in composite material A, the weight percentage of polymer A is 30-40 wt.%; the weight percentage of polymer B is 30-40 wt.%; the content of white oil is 20-40 wt.%; and the antioxidant is 0.3-0.4 wt.% of the content of composite material A. Even more preferably, in composite material A, the weight percentage of polymer A is 35-40 wt.%; the weight percentage of polymer B is 35-40 wt.%; the content of white oil is 20-30 wt.%; and the antioxidant is 0.3-0.4 wt.% of the content of composite material A. Within this preferred range, a material with high hardness, high light transmittance, and low haze can be obtained.

[0025] The present invention also provides a method for preparing the composition, wherein the components are mixed and then melted to obtain the composition.

[0026] The composition described in this invention can be obtained by melting using existing processes, for example, the steps of which are:

[0027] First, polymer A and polymer B are dried in an oven until the volatile content is less than 0.05%.

[0028] Then, polymer A and plasticizer oil, such as white oil, are placed in a high-speed mixer and mixed for 3-5 minutes, followed by the addition of other raw materials and mixed for another 3-5 minutes.

[0029] Finally, the mixed raw materials are fed into a screw extruder for granulation. The screw speed is 300-600 rpm and the temperature is 200-230℃.

[0030] The present invention also provides an application of the transparent thermoplastic elastomer composition with controllable hardness, which is used to prepare resin materials with high transparency and low haze; for example, it can be used to prepare thicker transparent products and transparent samples with complex structures, and has good application prospects.

[0031] Beneficial effects

[0032] This invention is based on the combination of special polymers A and B, which achieve synergistic effects, improving light transmittance and reducing haze, while also allowing for controllable material hardness. For example, the composition described in this invention has a light transmittance ≥85%, haze ≤5%, and hardness adjustable between 50 and 95 Shore A. It has significant application potential. Detailed Implementation

[0033] The following embodiments are used to describe in more detail the specific implementation of the present invention, so as to better understand the solution of the present invention and the advantages of its various aspects. The specific implementations and embodiments described below are for illustrative purposes only and are not intended to limit the present invention.

[0034] Example operation steps:

[0035] (1) Weigh out the raw materials polymer A, white oil, polymer B and antioxidant according to the weight ratio.

[0036] (2) Dry polymer A and polymer B in an oven until the volatile content is less than 0.05%;

[0037] (3) Put polymer A and white oil into a high-speed mixer and mix for 3-5 minutes, then add other raw materials and mix for 3-5 minutes;

[0038] (4) The mixed raw materials are put into a screw extruder for granulation. The screw speed is 300-600 rpm and the temperature is 200-230℃.

[0039] Performance testing:

[0040] Tensile strength and elongation at break: tested according to GB / T528-2009, tensile speed = 500 mm / min;

[0041] Hardness: Tested according to GB / T531.1-2008;

[0042] Melt flow index: GB / T3682.1-2018

[0043] Transmittance and haze: Tested according to GB / T 2410-2008, with a sample thickness of 2 mm and a C light source;

[0044] The raw material ratios and performance tests for Examples 1-6 are shown in Table 1;

[0045] Table 1: Formulation and Performance Test Results of Raw Materials Using YH-505, CBC-0510, and White Oil

[0046]

[0047]

[0048] The raw material ratios and performance tests for Examples 7-12 are shown in Table 2;

[0049] Table 2: Formulation and Performance Test Results of Raw Materials Using YH-530, CBC-1325X, and White Oil

[0050]

[0051]

[0052] In summary, the composition of the present invention can achieve synergy, obtain good light transmittance, unexpectedly improve haze, and effectively control hardness, bringing unexpected results.

Claims

1. A transparent thermoplastic elastomer composition with controllable hardness, characterized in that, It contains polymer A and polymer B; The polymer A is at least one of Baling Petrochemical's YH-505 and YH-530; The polymer B, manufactured by Formosa Plastics Corporation, is at least one of CBC0510 and CBC1325X. The polymer A is in the range of 1 to 99 parts by weight; The polymer B is present in parts by weight of 1 to 99 parts.

2. The transparent thermoplastic elastomer composition with controllable hardness as described in claim 1, characterized in that, The polymer A is present in parts by weight of 20 to 80; the polymer B is present in parts by weight of 20 to 80.

3. The transparent thermoplastic elastomer composition with controllable hardness as described in any one of claims 1 to 2, characterized in that, It also contains plasticizer oil.

4. The transparent thermoplastic elastomer composition with controllable hardness as described in claim 3, characterized in that, The plasticizing oil mentioned is white oil.

5. The transparent thermoplastic elastomer composition with controllable hardness as described in claim 3, characterized in that, The plasticizing oil mentioned is hydrogenated white oil.

6. The transparent thermoplastic elastomer composition with controllable hardness as described in claim 3, characterized in that, The plasticizing oil mentioned is 26# white oil.

7. The transparent thermoplastic elastomer composition with controllable hardness as described in claim 3, characterized in that, The plasticizing oil has a weight of less than or equal to 50 parts.

8. The transparent thermoplastic elastomer composition with controllable hardness as described in claim 7, characterized in that, The plasticizer oil is 20 to 40 parts by weight.

9. The transparent thermoplastic elastomer composition with controllable hardness as described in any one of claims 1 to 2, characterized in that, It also contains antioxidants.

10. The transparent thermoplastic elastomer composition with controllable hardness as described in claim 9, characterized in that, The antioxidant is present in parts by weight less than or equal to 1 part by weight.

11. The transparent thermoplastic elastomer composition with controllable hardness as described in claim 10, characterized in that, The antioxidant is present in a concentration of 0.1 to 0.5 parts by weight.

12. A method for preparing a transparent thermoplastic elastomer composition with controllable hardness according to any one of claims 1 to 11, characterized in that, The components are mixed and then smelted to obtain the product.

13. The application of a transparent thermoplastic elastomer composition with controllable hardness according to any one of claims 1 to 11, characterized in that, It is used to prepare resin materials with high transparency and low haze.

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