Low vocs, low odor, environmentally friendly material for passenger vehicle weatherseal production and method of making

Abstract

This invention discloses a low-VOCs, low-odor environmentally friendly material for the production of sealing strips for passenger vehicles and its preparation method, belonging to the field of polymer materials technology. The technical solution includes the following raw materials in parts by weight: 100 parts PVC resin; 5 parts stabilizer; 40-60 parts plasticizer; 0.4-0.6 parts lubricant; 1.3-1.5 parts antioxidant; 0.3-0.4 parts ultraviolet absorber; 0.3-0.5 parts deodorizer A; 0.8-1.0 parts deodorizer B; 10-25 parts light active calcium carbonate; 1.0-1.2 parts pigment; deodorizer A is a complex of zinc amino acid, and deodorizer B is benzoic anhydride-intercalated modified aluminum-magnesium hydrotalcite. This invention can capture free, irritating small-molecule alcohols and convert them into esters with milder odors, effectively preventing alcohols from being converted into irritating ethers and ketones during processing, thus reducing the odor and VOCs of passenger vehicle sealing strips.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a low-VOCs, low-odor environmentally friendly material for producing sealing strips for passenger vehicles and its preparation method. Background Technology

[0002] With increasing environmental awareness, people are becoming more demanding regarding the odor in their environment. As automobiles become a mainstream consumer product, the in-car environment has become a focal point for both vehicle manufacturers and consumers. The main sources of odor in cars are interior components such as car seats, floor mats, and weatherstripping, and these components widely utilize polyvinyl chloride (PVC) materials.

[0003] To meet usage requirements, polyvinyl chloride (PVC) must have appropriate amounts of additives, such as plasticizers, stabilizers, lubricants, and flame retardants. These additives emit a strong, pungent odor during interior use. If these irritating gases cannot be expelled from the vehicle interior in a timely manner, they can seriously affect the health of passengers.

[0004] One method to reduce VOCs and irritating odors is to add deodorizing agents (adsorbents) to the production formula. Patent CN107400317A uses W-55, W-66, PY88, Cel-Span E, diatomaceous earth, porous alumina, and activated carbon-based porous materials as odor adsorbents. Patent CN102911459B uses a composite odor absorbent, where the main component of the first odor absorbent is zinc ricinoleate, and the main component of the second odor absorbent is Na2O·Al2O3·γSiO2·γH2O. Patent CN105647060B also uses a composite deodorizing agent, mainly composed of 40-60 wt% (Z,Z)-9,12-octadecanoic acid zinc salt and 40-60 wt% (9Z,12R)-12-hydroxy-9-octadecanoic acid zinc salt. The deodorizer disclosed in patent CN111019266B is a compound of magnesium oxide modified polypyrrole and ethylene glycol glycidyl ether crosslinked chitosan gel.

[0005] The odor of PVC materials originates from PVC resin and various additives. Further research has revealed that the odor primarily comes from small-molecule alcohols in the additives and ethers and aldehydes formed from these alcohols during processing due to heating. Current deodorizers either rely on physical adsorption, which can lead to persistent odors, or they lack specificity and have poor deodorization effects. Therefore, it is necessary to develop suitable deodorizers for the production of low-odor vehicle sealing materials. Summary of the Invention

[0006] This invention provides a low-VOCs, low-odor environmentally friendly material for producing sealing strips for passenger vehicles. This material is a raw material for producing sealing strips for passenger vehicles and is the final material obtained by the preparation method of this invention. This material can capture free small molecules of alcohols, ethers, and ketones with irritating odors and convert them into esters with milder and less odor, thereby reducing the odor and VOCs of sealing strips for passenger vehicles.

[0007] The technical solution of this invention is as follows:

[0008] In the first aspect, a low-VOCs, low-odor environmentally friendly material for manufacturing sealing strips for passenger vehicles is disclosed, comprising the following raw materials in parts by weight:

[0009] The composition comprises: 100 parts PVC resin; 5 parts stabilizer; 40-60 parts plasticizer; 0.4-0.6 parts lubricant; 1.3-1.5 parts antioxidant; 0.3-0.4 parts ultraviolet absorber; 0.3-0.5 parts deodorizer A; 0.8-1.0 parts deodorizer B; 10-25 parts light active calcium carbonate; and 1.0-1.2 parts pigment. Deodorizer A is a complex of zinc amino acid, and deodorizer B is benzoic anhydride-intercalated modified aluminum-magnesium hydrotalcite. The PVC resin has an average degree of polymerization of 1000-2500, preferably PVC S-1300 produced by Qilu Petrochemical Company with an average degree of polymerization of 1300.

[0010] Preferably, the zinc amino acid complex is one of lysine zinc complex, glycine zinc complex, tryptophan zinc complex, and phenylalanine zinc complex, with lysine zinc complex being the most preferred; the stabilizer is a calcium zinc stabilizer, preferably AIMSTA-6802 from Shenzhen Zhihai Industrial Co., Ltd.

[0011] Preferably, the plasticizer is one or more of dioctyl terephthalate (DOTP), trioctyl trimellitate (TOTM), fatty acid polyester, and epoxidized soybean oil (ESBO), preferably a mixture of dioctyl terephthalate (DOTP) and epoxidized soybean oil (ESBO) in a mass ratio of 97:3.

[0012] Preferably, the lubricant is a low-density polyethylene oxidized wax lubricant, preferably Honeywell's AC-629A.

[0013] Preferably, the antioxidant is a phenolic antioxidant or a phosphorus-based antioxidant, and more preferably a phenolic antioxidant pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] (antioxidant 1010).

[0014] Preferably, the ultraviolet absorber is a benzotriazole ultraviolet absorber, more preferably 2-(2'-hydroxy-3',5'-ditert-butylphenyl)-5-chlorobenzotriazole (UV-327).

[0015] Preferably, the preparation method of deodorizer B is as follows: aluminum magnesium hydrotalcite is added to butanol, stirred and heated to 80℃~85℃, and a butanol solution of benzoic anhydride is added dropwise; after the addition is completed, stirring is continued for 50min~60min, and the butanol is removed by centrifugation; vacuum drying is performed to further remove the butanol solvent, thus obtaining deodorizer B.

[0016] Preferably, the pigment is prepared by mixing rutile titanium dioxide and pigment carbon black, wherein the mass of pigment carbon black is 5% to 6% of the mass of rutile titanium dioxide.

[0017] Secondly, a method for preparing the low-VOCs, low-odor environmentally friendly sealing strip material for passenger vehicles is disclosed, including the following steps:

[0018] 1) Add PVC resin, stabilizer, lubricant, antioxidant, UV absorber, deodorizer A and deodorizer B to a high-speed mixer and mix at a speed of 2200-2800 r / min. Heat to 80-85℃, add plasticizer, continue stirring and heat to 100-105℃, add light active calcium carbonate and pigment, continue stirring and heat to 125-130℃; transfer the material to a low-speed mixer at a speed of 200-500 r / min, and discharge the material when the temperature cools to 40-45℃.

[0019] 2) The mixed material from step 1) is granulated using a twin-screw extruder at a granulation temperature of 110℃~160℃ to obtain a low-VOCs, low-odor environmentally friendly material for passenger vehicle sealing strip production.

[0020] Compared with the prior art, the present invention has the following advantages:

[0021] 1. The low-VOCs, low-odor environmentally friendly passenger vehicle sealing strip production material prepared by this invention can capture free small molecules of alcohols, ethers and ketones with irritating odors and transform them into esters with milder and less odor, thereby reducing the odor and VOCs of passenger vehicle sealing strips and reducing the harm of harmful odors to the human body.

[0022] 2. The hydrotalcite modified with benzoic anhydride by deodorizer B and the amino acid zinc complex of deodorizer A can undergo esterification with alcohols (such as butanol and octanol) with strong odors remaining in plasticizers. This process converts alcohols into milder esters during processing, while preventing alcohols from being heated during processing and converting into more pungent ethers and ketones, thus reducing the odor of the sealing strips in passenger vehicles.

[0023] 3. Benzoic anhydride-modified hydrotalcite has a layered structure, which can effectively prevent unreacted alcohols from leaking out of the sealing strip, thereby reducing the odor and VOCs of passenger vehicle sealing strips.

[0024] 4. The deodorizing agent B, benzoic anhydride-modified hydrotalcite, and the deodorizing agent A, amino acid zinc complex have a synergistic effect, and the effect is better at a specific ratio.

[0025] 5. The plasticizer is a combination of DOTP and ESBO. DOTP itself is a high-performance plasticizer. When combined with epoxidized soybean oil, it can not only improve the mechanical properties and thermal stability of the material, but also has environmental advantages. It is a composite plasticizer solution with broad application prospects.

[0026] 6. The preparation method of the present invention ensures uniform mixing and full reaction of each component by controlling parameters such as the mixing sequence of raw materials, temperature, and rotation speed. This optimized production process not only improves production efficiency but also ensures the uniformity and stability of the final product and enhances the comprehensive performance of the materials used in production, such as thermal stability and aging resistance, thereby ensuring the stability and reliability of passenger vehicle sealing strips during long-term use. Detailed Implementation

[0027] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions in the embodiments of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0028] The PVC resin used is PVC S-1300, a polyvinyl chloride resin with an average degree of polymerization of 1300 produced by Qilu Petrochemical Company.

[0029] The stabilizer used is AIMSTA-6802, manufactured by Shenzhen Zhihai Industrial Co., Ltd.

[0030] The plasticizer is a compound of dioctyl terephthalate (DOTP) and epoxidized soybean oil (ESBO) in a mass ratio of 97:3.

[0031] The lubricant used is Honeywell AC-629A;

[0032] The antioxidant used is pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] (antioxidant 1010);

[0033] The ultraviolet absorber used is 2-(2'-hydroxy-3',5'-ditert-butylphenyl)-5-chlorobenzotriazole (UV-327);

[0034] Deodorizer A uses lysine zinc complex produced by Ningbo Yingqian Technology Co., Ltd.

[0035] Light activated calcium carbonate is produced by Changzhou Calcium Carbonate Co., Ltd.

[0036] The pigment is prepared by mixing rutile titanium dioxide and pigment carbon black, with the mass of pigment carbon black being 5% of the mass of rutile titanium dioxide.

[0037] The method for preparing the low-VOCs, low-odor environmentally friendly sealing strip material for passenger vehicles includes the following steps:

[0038] 1) Add PVC resin, stabilizer, lubricant, antioxidant, UV absorber, deodorizer A and deodorizer B to a high-low speed mixer and mix at 2500 r / min. Heat to 85°C, add plasticizer, continue stirring and heat to 105°C, add light active calcium carbonate and pigment, continue stirring and heat to 130°C; transfer the material to a low-speed mixer at 300 r / min, and discharge when the material temperature cools to 40°C.

[0039] 2) The mixed material from step 1) is granulated using a twin-screw extruder, with the process parameters set as follows:

[0040] Extruder temperature (°C): Zones 1, 2, 3, 4, 5 and the die head are 110, 120, 130, 140, 150 and 150 respectively, to obtain environmentally friendly materials for passenger vehicle sealing strips with low VOCs and low odor.

[0041] The mass fractions of each material added in Examples 1-5 are shown in Table 1.

[0042] Table 1

[0043]

[0044]

[0045] In Examples 1-5, the deodorizer B was prepared as follows: 100g of aluminum magnesium hydrotalcite was added to 200g of butanol, stirred and heated to 85°C, and 30g (calculated as pure benzoic anhydride) of butanol solution of benzoic anhydride (concentration of 30g / mL) was added dropwise; after the addition was completed, stirring was continued for 55min, and the butanol was removed by centrifugation; the mixture was dried under vacuum at 120°C to further remove the butanol solvent, thus obtaining deodorizer B.

[0046] The mass fractions of each material added in Examples 6-10 are shown in Table 2.

[0047] Table 2

[0048] Formulation components Example 6 Example 7 Example 8 Example 9 Example 10 PVC S-1 300 100 100 100 100 100 Calcium-zinc stabilizer 5 5 5 5 5 Plasticizer 50 45 55 47 52 Lubricant 0.5 0.6 0.6 0.5 0.4 Antioxidant 1.5 1.3 1.5 1.4 1.3 Ultraviolet absorber 0.3 0.4 0.3 0.4 0.4 Odor scavenger A 0.5 0.5 0.4 0.3 0.3 Odor scavenger B 1.0 0.8 0.9 1.0 1.0 Active light calcium carbonate 20 15 15 20 10 Pigment 1.1 1.1 1.0 1.2 1.2

[0049] In Examples 6-10, the deodorizer B was prepared as follows: 100g of aluminum magnesium hydrotalcite was added to 200g of butanol, stirred and heated to 85°C, and 25g (calculated as pure benzoic anhydride) of butanol solution of benzoic anhydride (concentration of 40g / mL) was added dropwise; after the addition was completed, stirring was continued for 55min, and the butanol was removed by centrifugation; the mixture was dried under vacuum at 120°C to further remove the butanol solvent, thus obtaining deodorizer B.

[0050] Comparative Example 1

[0051] Unlike Example 1, this comparative example does not include deodorizing agent A and deodorizing agent B, while the remaining materials and preparation methods are the same as in Example 1.

[0052] Comparative Example 2

[0053] Unlike Example 1, this comparative example does not include deodorizer A, and the amount of deodorizer B added is 1.40 parts. The remaining materials and preparation methods are the same as in Example 1.

[0054] Comparative Example 3

[0055] Unlike Example 1, this comparative example does not include deodorizing agent B, and the amount of deodorizing agent A added is 1.40 parts. The remaining materials and preparation methods are the same as in Example 1.

[0056] Comparative Example 4

[0057] Unlike Example 1, this comparative example does not include deodorizing agent A and deodorizing agent B, but instead includes 1.40 parts of zeolite. The remaining materials and preparation methods are the same as in Example 1.

[0058] Comparative Example 5

[0059] Unlike Example 2, the deodorizer B in this comparative example was prepared as follows: 100g of aluminum magnesium hydrotalcite was added to 200g of butanol, stirred and heated to 85°C, and 20g (calculated as pure benzoic anhydride) of butanol solution of benzoic anhydride (concentration of 30g / mL) was added dropwise; after the addition was completed, stirring was continued for 55min, and the butanol was removed by centrifugation; vacuum drying was carried out at 120°C to further remove the butanol solvent, thus obtaining deodorizer B. The remaining materials and preparation methods were the same as in Example 2.

[0060] Comparative Example 6

[0061] Unlike Example 1, the amount of deodorizing agent A added is 0.2 parts, while the remaining materials and preparation methods are the same as in Example 1.

[0062] Comparative Example 7

[0063] Unlike Example 1, the amount of deodorizer A added is 0.6 parts, while the remaining materials and preparation methods are the same as in Example 1.

[0064] Comparative Example 8

[0065] Unlike Example 1, the amount of deodorizing agent B added is 0.6 parts, while the remaining materials and preparation methods are the same as in Example 1.

[0066] Comparative Example 9

[0067] Unlike Example 1, the amount of deodorizing agent B added is 1.2 parts, while the remaining materials and preparation methods are the same as in Example 1.

[0068] Performance testing methods for the materials used in the production of sealing strips for passenger vehicles prepared in Examples 1-10 and Comparative Examples 1-9

[0069] (1) Raw material mixing: Add PVC resin, calcium-zinc stabilizer, lubricant, antioxidant, UV absorber and deodorizer to a high-speed and low-speed mixer and mix until the mixing temperature reaches 85°C. Add plasticizer and continue stirring to raise the temperature to 105°C. Add active light calcium carbonate and pigment and continue stirring to raise the temperature to 130°C. Place the material in a low-speed mixer and discharge it when the material temperature cools to 40°C.

[0070] (2) Granulation process: The mixed materials are granulated using a twin-screw extruder. The process parameters are set as follows:

[0071] Extruder temperature (°C): Zones 1, 2, 3, 4, 5 and the die head are 110, 120, 130, 140, 150 and 150 respectively.

[0072] (3) The materials for producing sealing strips for passenger vehicles prepared in Examples 1-10 and Comparative Examples 1-9 were plasticized by two-roll open milling, then pressed into 2mm thick samples by press, and then made into dumbbell-shaped samples for performance testing.

[0073] (4) Testing Standards: A. The tensile, aging, and thermal stability properties of the materials used in the production of sealing strips shall be tested in accordance with the requirements of GB / T21282-2007 "Rubber and Plastic Sealing Strips for Passenger Cars". B. The odor level shall be tested in accordance with the Volkswagen PV3900:2000-08 standard. The specified odor levels are: Level 1: Undetectable; Level 2: Detectable, without odor; Level 3: Noticeably detectable, but not very odorous; Level 4: Odor-causing; Level 5: Significantly odor-causing; Level 6: Unbearable.

[0074] The performance tests of the materials for producing passenger vehicle sealing strips prepared in Examples 1-10 and Comparative Examples 1-9 are shown in Table 3.

[0075] Table 3

[0076]

[0077] Compared to Example 1, in Examples 1-10, through the reasonable ratio of deodorizing agent A and deodorizing agent B, the two work synergistically, resulting in a final odor level of 1.5, significantly lower than the comparative example. Furthermore, the addition of deodorizing agents in Examples 1-10 did not affect physical properties such as tensile strength, elongation at break, thermal stability, and low-temperature catalytic temperature, ensuring the service life of the materials used in passenger vehicle sealing strip production. In Comparative Example 1, no deodorizing agents A and B were added; in Comparative Example 2, only deodorizing agent B was added; in Comparative Example 3, only deodorizing agent A was added; and in Comparative Example 4, porous zeolite, a conventional deodorizing agent, was used. The odor levels in Comparative Examples 1-4 were significantly lower. The odor levels were all very high, with a strong smell, affecting the user experience. In Comparative Example 5, the ratio of benzoic anhydride and aluminum-magnesium hydrotalcite was changed, resulting in insufficient benzoic anhydride between the aluminum-magnesium hydrotalcite layers, which failed to achieve the desired odor removal effect. In Comparative Example 6, the amount of odor remover A was too small, and in Comparative Example 8, the amount of odor remover B was also too small, both of which failed to achieve a good odor removal effect, mainly because they could not fully complex unreacted small molecules. In Comparative Example 7, the amount of odor remover A was too large, and in Comparative Example 9, the amount of odor remover B was too large. Although the odor removal effect was better, the excessive amount of odor remover led to higher material costs in production, which increased production costs.

[0078] Although the present invention has been described in detail by way of preferred embodiments, it is not limited thereto. Various equivalent modifications or substitutions can be made to the embodiments of the present invention by those skilled in the art without departing from the spirit and essence of the invention, and such modifications or substitutions should all be within the scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A low-VOCs, low-odor environmentally friendly material for producing sealing strips for passenger vehicles, characterized in that, The raw materials include the following parts by weight: 100 parts PVC resin; 5 parts stabilizer; 40-60 parts plasticizer; 0.4-0.6 parts lubricant; 1.3-1.5 parts antioxidant; 0.3-0.4 parts ultraviolet absorber; 0.3-0.5 parts deodorizer A; 0.8-1.0 parts deodorizer B; 10-25 parts light activated calcium carbonate; 1.0-1.2 parts pigment; The deodorizing agent A is a complex of zinc amino acid, and the deodorizing agent B is benzoic anhydride-intercalated modified aluminum-magnesium hydrotalcite.

2. The material for producing low-VOCs, low-odor environmentally friendly passenger vehicle sealing strips as described in claim 1, characterized in that, The zinc amino acid complex is one of lysine zinc complex, glycine zinc complex, tryptophan zinc complex, and phenylalanine zinc complex, and the stabilizer is a calcium zinc stabilizer.

3. The material for producing low-VOCs, low-odor environmentally friendly passenger vehicle sealing strips as described in claim 1, characterized in that, The plasticizer is one or more of dioctyl terephthalate, trioctyl trimellitate, fatty acid polyester, and epoxidized soybean oil.

4. The material for producing low-VOCs, low-odor environmentally friendly passenger vehicle sealing strips as described in claim 1, characterized in that, The lubricant is a low-density polyethylene oxidized wax lubricant.

5. The material for producing low-VOCs, low-odor environmentally friendly passenger vehicle sealing strips as described in claim 1, characterized in that, The antioxidant is a phenolic antioxidant or a phosphorus-based antioxidant.

6. The material for producing low-VOCs, low-odor environmentally friendly passenger vehicle sealing strips as described in claim 1, characterized in that, The ultraviolet absorber is a benzotriazole ultraviolet absorber.

7. The material for producing low-VOCs, low-odor environmentally friendly passenger vehicle sealing strips as described in claim 1, characterized in that, The specific preparation method of deodorizer B is as follows: aluminum magnesium hydrotalcite is added to butanol, stirred and heated to 80℃~85℃, and a butanol solution of benzoic anhydride is added dropwise; after the addition is completed, stirring is continued for 50min~60min, and butanol is removed by centrifugation; vacuum drying is performed to further remove butanol, thus obtaining deodorizer B.

8. The material for producing low-VOCs, low-odor environmentally friendly passenger vehicle sealing strips as described in claim 1, characterized in that, The pigment is prepared by mixing rutile titanium dioxide and pigment carbon black, and the mass of pigment carbon black is 5% to 6% of the mass of rutile titanium dioxide.

9. The method for preparing the low-VOCs, low-odor environmentally friendly passenger vehicle sealing strip material as described in any one of claims 1-8, characterized in that, Includes the following steps: 1) Add PVC resin, stabilizer, lubricant, antioxidant, UV absorber, deodorizer A and deodorizer B to a high-speed mixer and mix at a speed of 2200-2800 r / min. Heat to 80-85℃, add plasticizer, continue stirring and heat to 100-105℃, add light active calcium carbonate and pigment, continue stirring and heat to 125-130℃; Place the material into a low-speed mixer at a speed of 200-500 r / min, and discharge the material when the temperature of the material cools down to 40-45℃. 2) The mixed material from step 1) is granulated using a twin-screw extruder at a granulation temperature of 110℃~160℃ to obtain a low-VOCs, low-odor environmentally friendly material for passenger vehicle sealing strip production.

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