Polymer product enhanced deodorant master batch as well as preparation method and application thereof

Abstract

The invention discloses a macromolecular product enhanced deodorant master batch as well as a preparation method and application thereof. The macromolecular product enhanced deodorant master batch comprises the following raw material components: 20-30 parts of zinc benzenesulfinate; 10 to 20 parts of organic phosphonic acid; 5 to 10 parts of N, N-4, 4-diphenylmethane bismaleimide; 3 to 6 parts of N-(4-anilinophenyl) maleimide; 5-8 parts of methacrylic acid fatty alcohol; and 4-10 parts of an ethylene propylene diene monomer coating body, wherein the parts are parts by mass. The polymer product enhanced deodorant is a reactive pre-dispersed master batch deodorant, is easy to disperse, does not fly, is convenient to operate and store, can effectively remove or reduce toxic and harmful substances in rubber products and the like, improves the product quality, and promotes the improvement of mechanical properties and aging resistance at the same time.

Description

Technical Field

[0001] The invention relates to a polymer product enhanced deodorant masterbatch and a preparation method and application thereof, belonging to the technical field of polymer product enhanced deodorant. Background Art

[0002] Various high molecular substances such as rubber, plastic, thermoplastic elastomer, coating, paint, asphalt, etc., in addition to the main polymer, also have some low molecular substances and volatile compounding agents, and even reactive low molecular byproducts in the manufacturing or molding process, such as acetophenone, the decomposition product of DCP. Therefore, various high molecular substances or products will have different odors volatilized into the air during production and storage, including a large number of toxic substances, which seriously affect the air quality and have a great impact on human health. These volatile organic compounds contain many carcinogens. Toxic and harmful substances often have bad smells, which is also a reminder and protection for people.

[0003] The solutions in the prior art include: (1) placing the polymer material in a place where it takes a long time, and volatile substances will enter the air, causing pollution. (2) baking or boiling the polymer material, which will increase the process cost, cause product aging and reduce performance, and volatile substances will still enter the air, causing pollution. (3) using an adsorption deodorant for adsorption treatment, which can adsorb the gas to reduce volatilization and reduce odor, such as porous silicates (zeolite, bubble stone). However, the adsorption deodorant cannot be combined with the main material, otherwise it will lose the function of adsorbing odor, which is equivalent to impurities in the product, which will reduce product performance, and the odor molecules will evaporate again during the storage process of the product or when it is reheated. (4) using a masking agent. Adding a masking agent to the polymer can quickly cover the surface of the product to block the volatilization of odor molecules into the air, thereby reducing the odor. Such as the odor-free asphalt sold on the market (actually it should be called odor-masking asphalt). However, the odor molecules still exist in the product, and the odor molecules will evaporate again during the storage process or when the product is reheated. (5) Use a flavor-type deodorant, add various flavors to the product, and the fragrance evaporates quickly to cover up the odor. However, the fragrance covers up the odor, and the odor molecules still exist. The flavor brings out more odor molecules during the rapid volatilization process. As the storage time is extended, when the flavor evaporates, the product becomes more smelly and unpleasant. In short, the above-mentioned measures cannot fundamentally solve the odor of the product. There are also a few manufacturers that use reactive deodorants, which have the defects of poor compatibility and will destroy the mechanical properties of polymer materials to a certain extent. In addition, they are powders and are easy to fly and lose. At the same time, the deodorization effect is also limited and needs to be improved. To this end, the present application proposes a polymer product enhanced deodorant, its preparation method and its application, which is a deodorant masterbatch, which is not easy to fly and lose, is easy to process, good dispersion, easy to store, convenient to operate, and can fundamentally solve the harmful odor of polymer materials. Summary of the invention

[0004] The invention provides a polymer product enhanced deodorant, a preparation method and application thereof, which are used for enhancing the deodorization of polymer products.

[0005] In order to solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0006] A polymer product enhanced deodorant masterbatch, the raw material components of which include:

[0007] 20-30 parts of zinc benzenesulfinate;

[0008] 10-20 parts of organic phosphonic acid;

[0009] 5-10 parts of N,N-4,4-diphenylmethane bismaleimide;

[0010] 3-6 parts of N-(4-anilinophenyl)maleimide;

[0011] 5-8 parts of methacrylate fatty alcohol;

[0012] 4-10 parts of EPDM rubber coating, where the parts are by mass.

[0013] The polymer product enhanced deodorant masterbatch of the present application is a pre-dispersed masterbatch.

[0014] The above-mentioned polymer product enhanced deodorant masterbatch has an enhancing effect while removing odor. The reason is that the inventor believes that zinc benzenesulfinate contains active zinc atoms, which can bond with nitrogen, sulfur and other atoms in the odor. At the same time, N,N-4,4-diphenylmethane bismaleimide and N-(4-anilinophenyl) maleimide act as reactive additives, which combine with the aforementioned bonded active groups and react with rubber molecules to form a cross-linked structure, cross-linking low-molecular volatile substances into the rubber body, while thoroughly removing odors, it also has the effects of strengthening, toughening, and improving wear resistance. Organic phosphonic acids play an effective promoting role, which can maximize the effect of removing odors, and promote the improvement of mechanical properties and aging resistance. Safe and environmentally friendly.

[0015] The organic phosphonic acid is at least one of ethylenediaminetetramethylene phosphate, castor oil phosphate, diethylamine phosphate or 2,2′-methylene-bis(4,6-di-tert-butylphenoxy) sodium phosphate.

[0016] In order to improve the performance of polymer materials while removing odors, it is further preferred that the organic phosphonic acid is castor oil phosphate, which not only promotes the performance improvement, but also has a dispersion effect. Compared with other components, the performance improvement is more significant.

[0017] In order to ensure the dispersion effect while improving the compounding effect with other materials and achieve a better promotion effect, the methacrylate fatty alcohol is fatty alcohol polyoxyethylene ether methacrylate.

[0018] In order to further improve the stability of the deodorant and enhance the enhancement effect on polymer substances, the raw material components of the enhanced deodorant also include 3-5 parts of N,N-phenylene bismaleimide.

[0019] The method for preparing the above-mentioned polymer product enhanced deodorant masterbatch comprises the following steps:

[0020] 1) Mix all the raw materials, knead for 10-15 minutes at a temperature of 130-135°C and a pressure of 0.1-0.4MPa, and a rotor speed of 15-35rpm;

[0021] 2) calendering and grinding the material obtained in step 1) under the conditions of a calender roller surface temperature of less than 55° C., a pressure of 0.1-0.4 MPa, a roller distance of 0.01-0.02 mm, and a grinding flow rate of 5-6 kg / min; after calendering and grinding, the dispersibility of the prepared dispersed masterbatch in the rubber is significantly improved;

[0022] 3) The material obtained in step 2) is filtered through a 200-mesh filter and then granulated.

[0023] Step 2) produces a very thin sheet material.

[0024] The filtering in step 3) refers to the filtering after melting in the granulator and before pelletizing. The granulator has the function of integrating filtering and pelletizing. The 200-mesh filter is installed in the die head of the granulator, and pelletizing is performed after filtering. Filtration can remove impurities generated or brought in during material transportation.

[0025] The polymer product enhanced deodorant masterbatch is used for deodorizing and / or enhancing polypropylene or rubber.

[0026] The amount of the polymer product enhanced deodorant masterbatch used is 0.5-2.0% of the polymer product. More preferably, the amount of the polymer product enhanced deodorant used is 0.5-1.0% of the polymer product.

[0027] The rubbers suitable for the above polymer product enhanced deodorant masterbatch include NR, IR, SBR, BR, NBR or EPDM. NR refers to natural rubber. IR refers to isoprene rubber. SBR refers to styrene-butadiene rubber. BR refers to butadiene rubber. NBR refers to nitrile rubber. EPDM refers to ethylene-propylene-diene rubber.

[0028] When in use, the deodorant masterbatch is added to an internal mixer, an open mixer or a screw extruder, especially added together with the raw rubber in the front stage of internal mixing. The deodorant effect is better when the internal mixing temperature is 130℃-145℃.

[0029] % in this application, unless otherwise specified, are all mass percentages.

[0030] The technologies not mentioned in the present invention are all referred to the prior art.

[0031] Beneficial effects:

[0032] 1. This product is a reactive pre-dispersed masterbatch deodorizer, which is easy to disperse, does not fly, is easy to operate and store. It can effectively remove or reduce toxic and harmful substances in rubber products, improve product quality, and promote the improvement of mechanical properties and aging resistance.

[0033] 2. Solve the problems of collection and treatment of waste gas, volatile organic compounds and unorganized emissions generated in the production process of enterprises, and effectively solve the end-of-pipe treatment problems of toxic waste gas and volatile organic compounds generated in the production process of enterprises from the source, help enterprises achieve environmental protection exemptions, avoid production restrictions and shutdowns, save energy and reduce carbon emissions, and help enterprises achieve green and high-quality development.

[0034] 3. It can chelate with various harmful gases (such as benzene, toluene, xylene, ethylbenzene, styrene, formaldehyde, acetaldehyde, methacrolein, acetone, acetophenone, sulfur dioxide, hydrogen sulfide, ammonia, etc.) and cross-link in the rubber body, thereby greatly reducing volatility and migration, and fundamentally reducing or removing the odor of various rubber and plastic products;

[0035] 4. Applicable to various natural rubber and synthetic rubber products, thermoplastic elastomers, thermosetting plastic products, recycled rubber and recycled plastic products. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 The polymer product enhanced deodorant prepared in Example 1. DETAILED DESCRIPTION

[0037] In order to better understand the present invention, the content of the present invention is further explained below in conjunction with the embodiments, but the content of the present invention is not limited to the following embodiments.

[0038] If the temperature is not specifically mentioned in this application, it refers to room temperature (25±3°C).

[0039] Example 1

[0040] A polymer product enhanced deodorant, the raw materials of which are measured by weight: 25 parts of zinc benzenesulfinate; 15 parts of castor phosphate (Jiangsu Hai'an Petrochemical Plant, yellow-brown transparent oil); 8 parts of N,N-4,4-diphenylmethane bismaleimide; 5 parts of N-(4-anilinophenyl) maleimide; 6 parts of fatty alcohol polyoxyethylene ether methacrylate; 9 parts of ethylene propylene rubber (model AT2505N, brand Japan Mitsui Chemicals); 4 parts of N,N-m-phenylene bismaleimide.

[0041] The preparation method of fatty alcohol polyoxyethylene ether methacrylate in each example is: add p-toluenesulfonic acid and hydroquinone to a mixture of fatty alcohol polyoxyethylene ether (AEO-9, Jubang Chemical) and methacrylic acid at a molar ratio of 1:1.8, wherein the mass amount of p-toluenesulfonic acid is 1% of the mass of fatty alcohol polyoxyethylene ether, and the mass amount of hydroquinone is 0.2% of the mass of methacrylic acid, react at a temperature of 150°C for 5 hours, and use toluene as a water-carrying agent to obtain fatty alcohol polyoxyethylene ether methacrylate. Commercially available fatty alcohol polyoxyethylene ether methacrylate can also be used.

[0042] The method for preparing the polymer product enhanced deodorant comprises the following steps:

[0043] 1) All raw materials were mixed and kneaded for 10 minutes at a temperature of 130°C and a pressure of 0.3 MPa, with a rotor speed of 20 rpm;

[0044] 2) the material obtained in step 1) is calendered and milled under the conditions of a calender roller surface temperature of 45° C., a pressure of 0.3 MPa, a roller distance of 0.01 mm, and a milling flow rate of 5.6 kg / min; after the material is calendered and milled in this way, the dispersibility of the prepared dispersed masterbatch in the rubber is significantly improved;

[0045] 3) The material obtained in step 1) is filtered through a 200-mesh filter and granulated. Figure 1 As shown, Mooney viscosity, ML (1+4) @ 50 ℃: 50 ± 10; particle length 3-6mm, not connected, not agglomerated. Storage period at room temperature is more than 24 months, packed in lined plastic bags, cartons or paper bags, 25kg / bag.

[0046] Example 2

[0047] The difference from Example 1 is that castor oil phosphoric acid is replaced by sodium ethylenediaminetetramethylene phosphate, and the rest is the same as Example 1.

[0048] Example 3

[0049] The difference from Example 1 is that castor oil phosphoric acid is replaced by diethylamine phosphate, and the rest is the same as Example 1.

[0050] Example 4

[0051] The difference from Example 1 is that the raw material does not contain N,N-phenylene bismaleimide, and the rest is the same as Example 1.

[0052] Comparative Example 1

[0053] The difference from Example 1 is that zinc benzenesulfinate is replaced by zinc ricinoleate, and the rest is the same as Example 1.

[0054] Comparative Example 2

[0055] The difference from Example 1 is that fatty alcohol polyoxyethylene ether methacrylate is replaced by castor oil polyoxyethylene ester EL-40, and the rest is the same as Example 1.

[0056] Comparative Example 3

[0057] The difference from Example 1 is that N,N-4,4-diphenylmethane bismaleimide is omitted, and the rest is the same as Example 1.

[0058] Comparative Example 4

[0059] The difference from Example 1 is that N-(4-anilinophenyl)maleimide is omitted, and the rest is the same as Example 1.

[0060] Comparative Example 5

[0061] The difference from Example 1 is that N-(4-anilinophenyl)maleimide and N,N-4,4-diphenylmethanebismaleimide are omitted, and the rest are the same as Example 1.

[0062] Application Example 1

[0063] For polypropylene (melt index 50.00 g / 10 min, 0.91 g / cm 3 , flammable, melting point 165°C), the deodorant and polypropylene are blended and extruded into granules in a screw extruder, and the mass amount of the deodorant relative to the polypropylene is 0.5%.

[0064] Table 1 shows the analysis conditions of the release of volatile substances before and after the addition of deodorant

[0065]

[0066]

[0067] Table 2 Analysis results of volatile substance release of PP+0.5% deodorant

[0068]

[0069]

[0070] In the table, "blank" means no deodorant is added; Example 1 means the deodorant used is prepared by Example 1, and the rest are similar expressions and meanings; ND means not detected.

[0071] Table 3 shows the analysis conditions for the release of aldehydes and ketones before and after the addition of deodorants

[0072]

[0073] Table 4 Analysis results of the release of aldehydes and ketones from PP+0.5% deodorant

[0074]

[0075]

[0076] Table 5 Performance degradation of the deodorants obtained in each example after 500h UV aging test

[0077]

[0078] The attenuation ratio (%) in the table refers to the reduction rate of the removal effect of each deodorant on each volatile substance after the UV aging test compared to before the UV aging test. A test result less than 0.01% is considered to be 0.

[0079] Table 6 Improvement of tensile strength of polypropylene by deodorants obtained in various examples

[0080]

[0081] The strength improvement rate (%) in the table indicates the improvement rate of tensile strength after using the deodorant compared to the "blank" (before using the deodorant). A negative value (-) indicates a decrease, and a positive value (+ omitted) indicates an increase.

[0082] Application Example 2

[0083] For NBR (nitrile rubber), the raw material components include: NBR3305, 100 parts; white carbon black SiO2, 50 parts; polyethylene glycol PEG4000, 5.0 parts; plasticizer DOTP, 15 parts, calcium carbonate CaCO3, 20 parts, silane coupling agent CG-Si69, 1.0 parts; zinc oxide ZnO, 5.0 parts; stearic acid SA1801, 1.0; triallyl isocyanurate, 1.5 parts; antioxidant KY-445, 1.5 parts; deodorant (prepared in Example 1), 0-1 parts. Preparation method: all the above raw materials are added → mixing → 100" / section → cleaning → turning the material → unloading at 135-140℃.

[0084] Table 7 Vulcanization characteristics

[0085] Deodorant dosage Deodorant 0 0.5 parts of deodorant 1 deodorant ML,dNm 2.38 2.39 2.40 MH,dNm 19.22 18.94 18.65 TS1,S 41.50 48.30 48.30 TS2,S 61.50 68.40 64.60 TC10,S 58.40 65.40 61.60 TC90,S 141.80 140.10 148.30

[0086] Table 8 Physical properties test

[0087] Deodorant dosage Deodorant 0 0.5 parts of deodorant 1 deodorant Hardness, °A 60 61 61 Tensile strength, MPa 12.15 15.73 15.37 100% tensile stress, MPa 1.26 1.69 1.63 300% tensile stress, MPa 3.41 4.18 4.2 Elongation at break, % 458.26 526.51 525.27 Tear strength kgf / cm 57.47 64.87 63.42

[0088] Table 9 Odor test

[0089]

[0090]

[0091] Odor test standards: 1 no odor; 2 slight odor; 3 odor but not irritating; 4 irritating odor; 5 strong irritating odor; 6 unbearable odor.

[0092] Application Example 3

[0093] For EPDM (ethylene propylene diene monomer rubber), the raw material components include: EPDM756, 100 parts; carbon black N550, 100 parts; 32# rubber softening oil, 50 parts; Si69, 2.0 parts; Zn0, 5.0 parts; stearic acid SA1801, 1.0 parts; PEG4000, 2.0 parts; deodorant (prepared in Example 1), 0-1 parts. Preparation method: raw rubber → plasticizing → other all-in → mixing → cleaning → turning over → unloading at 140-145℃.

[0094] Table 10 Vulcanization characteristics

[0095] Deodorant dosage Deodorant 0 0.5 parts of deodorant 1 deodorant ML,dNm 1.61 1.46 1.50 MH,dNm 13.78 13.68 13.72 TS1,S 36.10 36.90 36.50 TS2,S 42.50 41.30 42.00 TC10,S 38.60 37.30 39.00 TC90,S 242.20 240.10 242.60

[0096] Table 11 Conventional physical property tests

[0097] Deodorant dosage Deodorant 0 0.5 parts of deodorant 1 deodorant Hardness, °A 56 57 56 Tensile strength, MPa 10.23 11.52 11.45 100% tensile stress, MPa 0.94 1.18 1.16 300% tensile stress, MPa 2.28 2.65 2.65 Elongation at break, % 392.16 450.79 451.39 Tear strength kgf / cm 24.83 28.78 28.59

[0098] Table 12 Odor test

[0099] Deodorant dosage Deodorant 0 0.5 parts of deodorant 1 deodorant Person 1 4 1 1 Person 2 4 1 1 Person 3 4 1 1

[0100] Odor test standards: 1 no odor; 2 slight odor; 3 odor but not irritating; 4 irritating odor; 5 strong irritating odor; 6 unbearable odor.

Claims

1. A polymer product enhanced deodorant masterbatch, characterized in that: Its raw material components include: The parts are by mass.

2. The polymer product enhanced deodorant masterbatch according to claim 1, characterized in that: The organic phosphonic acid is at least one of ethylenediaminetetramethylene phosphate, castor oil phosphate, diethylamine phosphate or 2,2′-methylene-bis(4,6-di-tert-butylphenoxy) sodium phosphate.

3. The polymer product enhanced deodorant masterbatch according to claim 3, characterized in that: The organic phosphonic acid is castor oil phosphate.

4. The polymer product enhanced deodorant masterbatch according to any one of claims 1 to 3, characterized in that: The methacrylate fatty alcohol is fatty alcohol polyoxyethylene ether methacrylate.

5. The polymer product enhanced deodorant masterbatch according to any one of claims 1 to 3, characterized in that: It also includes 3-5 parts of N,N-phenylene bismaleimide.

6. A method for preparing a polymer product enhanced deodorant masterbatch according to any one of claims 1 to 3, characterized in that: The steps include: 1) Mix all the raw materials, knead for 10-15 minutes at a temperature of 130-135°C and a pressure of 0.1-0.4MPa, and a rotor speed of 15-35rpm; 2) calendering and milling the material obtained in step 1) under the conditions of a calender roller surface temperature of less than 55° C., a pressure of 0.1-0.4 MPa, a roller distance of 0.01-0.02 mm, and a milling flow rate of 5-6 kg / min; 3) The material obtained in step 2) is filtered through a 200-mesh screen and granulated.

7. An application of a polymer product enhanced deodorant masterbatch according to any one of claims 1 to 3, characterized in that: Application of polymer product enhancement deodorant for deodorization and / or enhancement of polypropylene or rubber.

8. The use of the polymer product enhanced deodorant masterbatch as claimed in claim 7, characterized in that: The dosage of the polymer product enhanced deodorant is 0.5-2.0% of the polymer product.

9. The use of the polymer product enhanced deodorant masterbatch as claimed in claim 8, characterized in that: The dosage of the polymer product enhanced deodorant is 0.5-1.0% of the polymer product.

10. The use of the polymer product enhanced deodorant masterbatch according to any one of claims 7 to 9, characterized in that: The rubber includes NR, IR, SBR, BR, NBR and / or EPDM.

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