A sbs resin and its use in the production of tpee composites

Abstract

The application discloses a kind of SBS resin and its application in preparation TPEE composite material, belong to high polymer engineering plastics technical field;SBS resin provided by the application includes the following quality parts of raw materials: 80 parts hydrogenated SBS resin, 0.8-1.5 parts trimethyl allyl isocyanate, 0.5-1 parts 2,5-dimethyl-2,5-bis (tert-butyl peroxide) hexane, 15-25 parts paraffin oil, 1-3 parts lubricant.SBS resin provided by the application is applied to the preparation of TPEE composite material, and the TPEE composite material obtained has excellent fluidity and mechanical strength, and also has lower glossiness grade.

Description

Technical Field

[0001] This invention belongs to the field of polymer engineering plastics technology, and particularly relates to an SBS resin and its application in the preparation of TPEE composite materials. Background Technology

[0002] TPEE (Thermoplastic Polyester Elastomer) is a high-performance engineering-grade elastomer that combines the elasticity of rubber with the strength of engineering plastics, while also possessing the processing ease of thermoplastics. It exhibits excellent heat and chemical resistance, as well as a pleasant feel, and is frequently used for molding parts that come into contact with the human body. Due to its superior feel, TPEE material shows promise for applications in covering surfaces such as seats, automotive door panels, and dashboard panels. However, conventional TPEE materials suffer from high gloss and low flowability, leading to issues with the appearance and molding of the finished parts. Current technologies address these problems by adding fillers to TPEE materials; however, the introduction of fillers reduces the mechanical strength of the TPEE material. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide an SBS resin that, when applied to the preparation of TPEE composite materials, enables the TPEE composite materials to have excellent flowability, a low gloss level, and superior mechanical strength, and its application in the preparation of TPEE composite materials.

[0004] To achieve the above objectives, in a first aspect, the present invention provides an SBS resin comprising the following raw materials in parts by weight:

[0005] 80 parts hydrogenated SBS resin, 0.8-1.5 parts trimethylallyl isocyanate, 0.5-1 part 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 15-25 parts paraffin oil, and 1-3 parts lubricant.

[0006] The SBS resin provided by this invention uses hydrogenated SBS resin as a raw material, and simultaneously selects 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and hydrogenated SBS resin to undergo a crosslinking reaction under the action of a specific crosslinking agent. In addition, appropriate amounts of paraffin oil and lubricant are added. The resulting SBS resin has low flowability and a unique chain structure. Therefore, when it is subsequently applied to the preparation of TPEE composite materials, it can form a micro-island structure with TPEE resin, thereby reducing the macroscopic gloss of TPEE composite materials, while retaining the excellent mechanical strength and good flowability of TPEE.

[0007] This invention does not have any special requirements for the hydrogenation rate of the hydrogenated SBS resin; any rate within the conventional range in the field is acceptable.

[0008] For example, the hydrogenation rate of the hydrogenated SBS resin can be 40-60%; the test method for the hydrogenation rate is as follows: the sample is scanned using a nuclear magnetic resonance analyzer to obtain a nuclear magnetic resonance spectrum, and the relative content of unsaturated double bonds in the sample is calculated by integrating the area of ​​each structural characteristic peak in the spectrum, thereby further calculating the degree of hydrogenation.

[0009] This invention does not impose any particular limitation on the viscosity of the paraffin oil; any viscosity range conventionally used in the art is acceptable. For example, the viscosity of the paraffin oil at 40°C can be 5-110 mmHg. 2 / s.

[0010] The present invention does not impose any particular limitation on the choice of lubricant; any lubricant conventionally used in the art is acceptable. Exemplarily, the lubricant includes at least one of silicone, silicone oil, and erucamide.

[0011] As a preferred embodiment of the SBS resin of the present invention, the viscosity of the 20wt% toluene solution of the hydrogenated SBS resin is 500-1200 Pa·s.

[0012] It should be noted that the viscosity of the 20wt% toluene solution of the hydrogenated SBS resin was obtained by testing in accordance with the standard Q / SH1085130-2006.

[0013] For example, the viscosity of the 20wt% toluene solution of the hydrogenated SBS resin can be any point value or any two points between 500-1200 Pa·s, such as 600-1000 Pa·s, or 500 Pa·s, 550 Pa·s, 600 Pa·s, 650 Pa·s, 700 Pa·s, 750 Pa·s, 800 Pa·s, 850 Pa·s, 900 Pa·s, 950 Pa·s, 1000 Pa·s, etc.

[0014] In a second aspect, the present invention provides a method for preparing the SBS resin, the method comprising the following steps: mixing the components uniformly and then melt-extruding to obtain the SBS resin.

[0015] In a preferred embodiment of the preparation method described in this invention, the twin-screw extruder has a length-to-diameter ratio ≥ 56:1, a screw speed of 350-450 r / min, and a temperature of 120-180℃ during melt extrusion.

[0016] In a third aspect, the present invention provides a TPEE composite material comprising the following components in parts by weight:

[0017] 58-82 parts TPEE resin, 8-32 parts SBS resin as described in this invention, 4-16 parts maleic anhydride graft, and 0-1 parts additives.

[0018] The TPEE composite material provided by this invention achieves good mechanical strength, low gloss, and excellent flowability by selecting appropriate mass fractions of components and ensuring excellent interaction between the components.

[0019] Specifically, this invention selects to add the SBS resin described in this invention to TPEE resin. The two have excellent compatibility under the action of maleic anhydride grafts, which can effectively form a micro-island structure, thereby reducing the macroscopic gloss. Furthermore, the SBS resin of this invention has a specific chain structure, which can interact with TPEE resin and compatibilizer to improve the flowability of TPEE composite material and retain the good mechanical strength of TPEE composite material.

[0020] The TPEE resin content is ≥54% of the total mass of the TPEE composite material.

[0021] Preferably, the mass percentage of TPEE resin is 60-78% based on the total mass of the TPEE composite material.

[0022] For example, the mass fraction of the TPEE resin can be any point value or any two points within a range of 58-82 parts, such as 60-80 parts, or 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82 parts, etc.; the mass fraction of the SBS resin can be any point value or any two points within a range of 8-32 parts, such as 10-30 parts, or 8, 10, 12, 15, 18 parts, etc. 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, etc.; the maleic anhydride graft can be any point value or any two-point range value between 4 and 16 parts, for example, it can be 5-15 parts, or it can be 4 parts, 5 parts, 7 parts, 9 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, etc.; the adjuvant can be any point value or any two-point range value between 0 and 1 part, for example, it can be 0 parts, 0.3 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, etc.

[0023] The TPEE resin described in this invention can be purchased commercially or prepared in-house. In-house preparation can be carried out using conventional methods.

[0024] Preferably, in the preparation process of the TPEE resin, the hard segment monomer can be terephthalic acid and butanediol, and the soft segment monomer can be butanediol.

[0025] Preferably, the preparation method of the TPEE resin includes the following steps: mixing terephthalic acid (PTA), benzoic acid (BA), butanediol (BG) and tetrahydrofuran polyether (PTMG), then adding tetrabutyl titanate and heating in a closed environment for reaction, after the heating and closed reaction is completed, reducing the pressure and continuing to raise the temperature for reaction, and cooling to room temperature after the reaction is completed to obtain TPEE resin.

[0026] Preferably, the molar ratio of terephthalic acid, benzoic acid, butanediol and tetrahydrofuran polyether is 1:(0.1-2):(1-2):(0.01-0.05).

[0027] Preferably, the mass percentage of tetrabutyl titanate is 0.01-0.03% based on the total mass of terephthalic acid, benzoic acid, butanediol and tetrahydrofuran polyether.

[0028] Preferably, the temperature of the heating and sealing reaction is 220-240℃ and the time is 2.5-3.5h.

[0029] Preferably, the temperature of the heating reaction is 245-255℃ and the time is 2.5-3.5h.

[0030] Preferably, the pressure reduction is to reduce the pressure to 80-120 Pa.

[0031] It should be noted that different melt indices of TPEE resin can be prepared by adjusting the amount of benzoic acid added to the reaction raw materials.

[0032] Preferably, in the TPEE resin, the molar ratio of hard segment (polybutylene terephthalate) to soft segment (polytetrahydrofuran ether) is 1:(0.85-0.95).

[0033] It should be noted that the molar ratio of hard segments to soft segments in the TPEE resin can be obtained by 1H NMR spectroscopy.

[0034] As a preferred embodiment of the TPEE composite material of the present invention, the TPEE composite material comprises the following components in parts by weight: 65-72 parts TPEE resin, 18-22 parts SBS resin of the present invention, 8-12 parts maleic anhydride graft, and 0-1 parts additives.

[0035] This invention has found that the mass fraction of a component can affect the overall performance of a product to some extent. When the mass fraction of the component is further selected within the above-mentioned range, the overall performance of the resulting product is even better.

[0036] As a preferred embodiment of the TPEE composite material of the present invention, the TPEE resin has a melt index of 90-140 g / 10 min at 230°C / 2.16 kg.

[0037] It should be noted that the melt index of the TPEE resin was obtained by testing in accordance with ISO 1133-1-2011, and the test conditions were 230℃ / 2.16kg.

[0038] For example, the melt index of the TPEE resin at 230℃ / 2.16kg can be any point value or any two-point range value between 90-140g / 10min, such as 100-130g / 10min, or 90g / 10min, 95g / 10min, 100g / 10min, 105g / 10min, 110g / 10min, 115g / 10min, 120g / 10min, 125g / 10min, 130g / 10min, 135g / 10min, 140g / 10min, etc.

[0039] In a preferred embodiment of the TPEE composite material of the present invention, the grafting rate of the maleic anhydride graft is 0.4-1.6%.

[0040] It should be noted that the grafting rate of the maleic anhydride graft is measured by titration. Specifically, the purified graft is accurately weighed, added to xylene, heated under reflux until completely dissolved, cooled, neutralized with KOH-ethanol standard solution, and then titrated with HCl-isopropanol standard solution until pink. The volume consumed is recorded, and the grafting rate is calculated using the formula.

[0041] For example, the grafting rate of the maleic anhydride graft can be any point value or any two points between 0.4% and 1.6%, such as 0.5%-1.5%, 0.5%-1%, 1%-1.5%, etc., or 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, etc.

[0042] Preferably, the grafting rate of the maleic anhydride graft is 0.8-1.2%.

[0043] This invention has found that maleic anhydride grafts with different grafting rates have a certain impact on the compatibility of TPEE resin and SBS resin. When the grafting rate of maleic anhydride grafts is further selected to be 0.4-1.6%, especially 0.8-1.2%, the resulting product has higher mechanical strength, better flowability, and lower gloss level.

[0044] As a preferred embodiment of the TPEE composite material of the present invention, the maleic anhydride graft includes at least one of maleic anhydride grafted SEBS and maleic anhydride grafted PP.

[0045] In a preferred embodiment of the TPEE composite material of the present invention, the additives include light stabilizers and antioxidants.

[0046] Preferably, the light stabilizer includes hindered amine light stabilizers and triazine light stabilizers.

[0047] More preferably, the mass ratio of hindered amine light stabilizer to triazine light stabilizer in the light stabilizer is 3:2.

[0048] For example, the hindered amine light stabilizer includes at least one of light stabilizer 622, light stabilizer 944, light stabilizer 783, light stabilizer 3853, light stabilizer 292, and light stabilizer 123; the triazine light stabilizer includes at least one of UV-234, UV-236, and UV-237.

[0049] For example, the antioxidant includes at least one of antioxidant 1010, antioxidant 1076, antioxidant 1790, antioxidant 168, antioxidant DLTP, and antioxidant 626.

[0050] In a fifth aspect, the present invention provides a method for preparing the TPEE composite material, the method comprising the following steps:

[0051] After drying, the raw materials are weighed and mixed, then fed into a twin-screw extruder. After extrusion, stranding, cooling, pelletizing, and drying, TPEE composite material is obtained.

[0052] In a preferred embodiment of the preparation method described in this invention, the twin-screw extruder has a length-to-diameter ratio ≥ 56:1, a screw speed of 400-500 r / min, and a temperature of 120-200℃ during melt extrusion.

[0053] In a sixth aspect, the present invention provides the application of the TPEE composite material in the preparation of automotive injection-molded skin parts.

[0054] For example, the TPEE composite material is used in the fabrication of skins for automobile seats, automobile door panels, and dashboards.

[0055] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0056] This invention provides an SBS resin obtained by selecting hydrogenated SBS resin as a raw material and simultaneously selecting 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and hydrogenated SBS resin to undergo a crosslinking reaction under the action of a specific crosslinking agent. Additionally, appropriate amounts of paraffin oil and lubricant are added. The resulting SBS resin exhibits low flowability and a unique chain structure. Therefore, when subsequently applied to the preparation of TPEE composites, it can form a micro-island structure with TPEE resin under the action of maleic anhydride grafts, thereby reducing the macroscopic gloss of the TPEE composite, improving its flowability, and retaining the excellent mechanical strength of TPEE. Furthermore, the preparation method of the SBS resin and TPEE resin provided by this invention is simple to operate and beneficial for practical production applications. Detailed Implementation

[0057] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0058] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in the field.

[0059] Hydrogenated SBS resin 1: ZL-Q5501, hydrogenation rate 40%, viscosity of 20wt% toluene solution 600 Pa·s, Zhongli Technology;

[0060] Hydrogenated SBS resin 2: ZL-Q5503, hydrogenation rate 60%, viscosity of 20wt% toluene solution is 1000 Pa·s, Zhongli Technology;

[0061] TPEE resin 1: melt index of 130 g / 10 min, self-made;

[0062] TPEE resin 2: melt index of 100g / 10min, self-made;

[0063] Maleic anhydride graft 1: G622, maleic anhydride grafted onto SEBS, grafting rate 1.0%, Nengzhiguang;

[0064] Maleic anhydride graft 2: G873, maleic anhydride grafted onto SEBS, grafting rate 0.5%, Nengzhiguang;

[0065] Maleic anhydride graft 3: G531, maleic anhydride grafted onto SEBS, grafting rate 1.5%, Nengzhiguang;

[0066] Maleic anhydride graft 4: AD-105, maleic anhydride grafted onto PP, grafting rate 0.8%, Bochen;

[0067] Paraffin oil: 500N, Formosa Plastics;

[0068] Lubricant: Silicone, MB50-002, Dow Corning;

[0069] Light stabilizer: A mixture of light stabilizer 944 and light stabilizer UV-234 in a mass ratio of 3:2. Light stabilizer 944 and light stabilizer UV-234 are commercially available.

[0070] Antioxidant: Antioxidant 1010, commercially available.

[0071] The preparation method of TPEE resin 1 includes the following steps: Terephthalic acid (PTA), benzoic acid (BA), butanediol (BG), and tetrahydrofuran polyether (PTMG, molar mass 2000 g / mol) are prepared. PTA, BA, BG, and PTMG are added to a reaction vessel in a molar ratio of 1:0.2:1.5:0.02. Two-thousandths of the raw material weight of tetrabutyl titanate is added, and the mixture is heated to 230°C and reacted under sealed conditions for 3 hours. Subsequently, the pressure inside the vessel is reduced to 100 Pa, and the temperature is raised to 250°C for another 3 hours. After the reaction is completed, the mixture is cooled to room temperature to obtain TPEE resin 1.

[0072] The melt index of TPEE resin 2 can be changed by adjusting the amount of BA added.

[0073] The light stabilizer, antioxidant, lubricant, trimethylallyl isocyanate, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane used in the parallel experiments of the examples and comparative examples were kept consistent.

[0074] Examples 1-4 and Comparative Examples 1-2

[0075] The present invention provides an SBS resin in the embodiments and comparative examples, wherein the raw material content (parts by weight) of the SBS resin is shown in Table 1.

[0076] Table 1

[0077] Hydrogenated SBS resin 1 80 80 80 80 80 Hydrogenated SBS resin 2 80 Trimethylallyl isocyanate 1 0.8 1.5 1 1 dicumyl peroxide 1 2,5-Dimethyl-2,5-bis(tert-butylperoxy)hexane 0.8 1 0.5 0.8 0.8 Benzoyl peroxide 0.8 paraffin oil 20 15 25 20 20 20 lubricant 2 1 3 2 2 2

[0078] The preparation method of SBS resin provided in Example 1 includes the following steps: hydrogenated SBS, trimethylallyl isocyanate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and lubricant are mixed and added to the main feed port of a twin-screw extruder; paraffin oil is added to the third section of the twin-screw extruder barrel; the mixture is melted, mixed, extruded, and granulated; wherein the length-to-diameter ratio of the screw of the twin-screw extruder is 56:1, the screw speed is 400 r / min, and the temperatures of each section are 80℃, 180℃, 200℃, 200℃, 200℃, 200℃, 200℃, and 220℃, respectively;

[0079] The methods for preparing SBS resins provided in Examples 2-4 and Comparative Examples 1-2 are identical to those in Example 1.

[0080] The SBS resins prepared in Examples 1-4 were named SBS resin AD, and the SBS resins prepared in Comparative Examples 1-2 were named SBS resin ab.

[0081] Application Example 1-10 and Comparative Application Example 1-3

[0082] The present invention provides a TPEE complex in application examples and comparative application examples, wherein the component content (parts by weight) of the TPEE complex is shown in Table 2-3;

[0083] Table 2

[0084] TPEE resin 1 70 60 80 / 70 70 70 TPEE resin 2 / / / 70 / / / SBS resin A 20 30 10 20 / / / SBS resin B / / / / 20 / / SBS resin C / / / / / 20 / SBS resin D / / / / / / 20 Maleic anhydride graft 1 10 5 15 10 10 10 10 Light stabilizers 0.3 0 0.3 0.3 0.3 0.3 0.3 antioxidants 0.3 0 0.3 0.3 0.3 0.3 0.3

[0085] Table 3

[0086] TPEE resin 1 70 70 70 70 70 70 SBS resin A 20 20 20 / / / SBS resin a / / / 20 / / SBS resin b / / / / 20 / Hydrogenated SBS resin 1 / / / / / 20 Maleic anhydride graft 1 / / / 10 10 10 Maleic anhydride graft 2 10 / / / / / Maleic anhydride graft 3 / 10 / / / / Maleic anhydride graft 4 / / 10 / / / Light stabilizers 0.3 0.3 0.3 0.3 0.3 0.3 antioxidants 0.3 0.3 0.3 0.3 0.3 0.3

[0087] The preparation method of the TPEE composite material provided in Application Example 1 includes the following steps: weighing and mixing the dried raw materials and feeding them into a twin-screw extruder, extruding, drawing, cooling, pelletizing and drying to obtain the TPEE composite material; wherein the length-to-diameter ratio of the screw of the twin-screw extruder is 56:1, the screw speed is 450 r / min, and the temperatures of each section are 80℃, 180℃, 220℃, 220℃, 220℃, 220℃, 220℃ and 230℃ respectively;

[0088] The preparation methods of the TPEE composite materials provided in Application Examples 2-10 and Comparative Application Examples 1-3 are consistent with those in Application Example 1.

[0089] Example of effect

[0090] The performance of the TPEE composite materials prepared by the present invention in the effect examples, application examples, and comparative application examples includes the following aspects:

[0091] 1. Melt Flow Index: Tested according to ISO 1133-1-2011 standard method, test conditions are 230℃ / 1.2kg; the melt flow index for injection molded skin parts should be ≥100g / 10min.

[0092] 2. Tensile strength test: Tested according to ISO 37-2017 standard, at 500 mm / min. The tensile strength should be ≥6 MPa to meet the application requirements of injection molded skin parts.

[0093] 3. Gloss test: Tested according to ISO 2813-2014 standard, examine the gloss level at 60° on a uniform plane, and meet the application requirements of injection molded skin parts, the gloss level should be <1.2;

[0094] The results are shown in Table 4.

[0095] Table 4

[0096]

[0097] As can be seen from Table 4, when the technical solution provided by the present invention is adopted, the obtained TPEE composite material has excellent flowability and mechanical strength, and also has low gloss. Specifically, the melt index of the obtained TPEE composite material is above 102 g / 10 min, the tensile strength is above 7.2 MPa, and the gloss is below 1.1. That is, the TPEE composite material prepared by the technical solution provided by the present invention meets the application requirements of injection molded skin parts.

[0098] As can be seen from Application Examples 1, 5-7, and Comparative Application Examples 1-3, the type of SBS resin added to the TPEE composite material affects the overall performance of the product. When the crosslinking agent used in the SBS resin in Comparative Application Example 1 is not the type used in this invention, the resulting TPEE composite material has a very high gloss. When the raw material used in the SBS resin in Comparative Application Example 2 is not 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane used in this invention, the melt index and tensile strength of the resulting TPEE composite material are significantly reduced. When hydrogenated SBS is used directly in Comparative Application Example 3, the resulting product has a very high gloss.

[0099] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An SBS resin, characterized in that, The SBS resin comprises the following raw materials in parts by weight: 80 parts hydrogenated SBS resin, 0.8-1.5 parts trimethylallyl isocyanate, 0.5-1 part 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 15-25 parts paraffin oil, and 1-3 parts lubricant.

2. The SBS resin according to claim 1, characterized in that, The viscosity of the 20wt% toluene solution of the hydrogenated SBS resin is 500-1200 Pa·s.

3. The method for preparing SBS resin as described in claim 1 or 2, characterized in that, The preparation method includes the following steps: mixing the components evenly and then melting and extruding to obtain SBS resin.

4. A TPEE composite material, characterized in that, The TPEE composite material comprises the following components in parts by weight: 58-82 parts TPEE resin, 8-32 parts The SBS resin as described in claim 1 or 2, 4-16 parts of maleic anhydride graft, and 0-1 parts of additives.

5. The TPEE composite material according to claim 4, characterized in that, The TPEE composite material comprises the following components in parts by weight: 65-72 parts TPEE resin, 18-22 parts SBS resin as described in claim 1 or 2, 8-12 parts maleic anhydride graft, and 0-1 parts additives.

6. The TPEE composite material according to claim 4, characterized in that, The melt flow index of the TPEE resin at 230℃ / 2.16kg is 90-140g / 10min.

7. The TPEE composite material according to claim 4, characterized in that, The grafting rate of the maleic anhydride graft is 0.4-1.6%.

8. The TPEE composite material according to claim 4, characterized in that, The maleic anhydride graft includes at least one of maleic anhydride-grafted SEBS and maleic anhydride-grafted PP.

9. The method for preparing the TPEE composite material according to any one of claims 4-8, characterized in that, The preparation method includes the following steps: weighing the dried raw materials and mixing them, feeding them into a twin-screw extruder, and then extruding, stretching, cooling, pelletizing, and drying to obtain TPEE composite material.

10. The application of the TPEE composite material as described in any one of claims 4-8 in the preparation of automotive injection-molded skin parts.

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