High-elasticity high-pressure impact-resistant wear-resistant rubber carpet and preparation process

Abstract

The invention relates to the technical field of carpets, and discloses a high-elasticity high-pressure impact-resistant wear-resistant rubber carpet and a preparation process thereof.The rubber carpet sequentially comprises a chemical fiber layer, a non-woven fabric layer and a rubber layer from top to bottom, the rubber composition is prepared by taking chloroprene rubber, butadiene styrene rubber and the like as base materials and modified aramid fibers and the like as auxiliary materials through banburying and extrusion processes, and the modified aramid fibers are prepared by modifying macromolecular substances which are alternately connected by ferrocene-fluoromethyl benzene and are connected by ester bonds on the surfaces of the aramid fibers. And due to the existence of the aramid fibers, the stamping resistance and wear resistance of the rubber layer can be effectively improved. Secondly, ferrocene, a rigid benzene ring structure, fluorine elements and silicon-oxygen bonds generated by substitution reaction contained in a macromolecular substance structure can improve the high-temperature resistance of the carpet, and meanwhile, the carpet is endowed with self-cleaning performance.

Description

Technical Field

[0001] The present invention relates to the technical field of carpets, in particular to a high-elasticity, high-pressure, impact-resistant, wear-resistant rubber carpet and a preparation process thereof. Background Art

[0002] As an important branch of modern floor materials, the technological evolution of carpets has always revolved around "functionality" and "scenario adaptability". With the continuous development of science and technology, the performance requirements of carpets have expanded from single anti-slip to a composite system of high elasticity, impact resistance and wear resistance.

[0003] Compared to conventional fabric carpets, rubber carpets possess greater elasticity due to their unique molecular chain structure. For example, the cis-1,4-polyisoprene segments of natural rubber can undergo reversible deformation under stress, with elongation reaching 1000% and elastic recovery exceeding 80%. This property enables rubber carpets to form an "energy buffer" under dynamic loads: when pressure is applied by a person or an object, the molecular chains absorb the impact energy through a curling-stretching motion; after the pressure is released, the segments quickly return to their original shape, avoiding permanent deformation. However, rubber carpets have poor impact resistance and poor wear resistance, resulting in a relatively short service life.

[0004] Currently, the impact resistance and wear resistance of rubber carpets can be improved to a certain extent by adding inorganic additives to the formula. However, there is a significant interface incompatibility between the inorganic additives and the rubber substrate itself. This easily results in a problem where a small amount of addition has no significant effect, while a large amount of addition leads to a negative impact on the mechanical strength of the rubber. Based on this, the present invention provides a rubber carpet with good comprehensive performance, which not only solves the problems existing in the prior art, but also has the advantages of being easy to clean and resistant to high temperatures. Summary of the Invention

[0005] In order to solve the problems mentioned in the background technology, the purpose of the present invention is to provide a high-elasticity, high-pressure, impact-resistant and wear-resistant rubber carpet and a preparation process.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A high-elasticity, high-pressure, impact-resistant, wear-resistant rubber carpet, comprising, from top to bottom, a chemical fiber layer, a non-woven fabric layer, and a rubber layer;

[0008] The rubber layer is made by melting and extruding the rubber composition and then forming it by extrusion;

[0009] The rubber composition includes the following components measured in parts by weight:

[0010] 60-70 parts of chloroprene rubber, 50-60 parts of styrene-butadiene rubber, 40-50 parts of natural rubber, 25-35 parts of thermoplastic polyurethane elastomer, 10-20 parts of ethylene-vinyl acetate copolymer, 3-6 parts of modified aramid fiber, 0.1-0.3 parts of benzoyl peroxide, 50-70 parts of white oil, 4-8 parts of silane coupling agent, and 5-10 parts of inorganic additives.

[0011] As a further embodiment of the present invention, the method for preparing the modified aramid fiber comprises the following steps:

[0012] Step 1: Functionalization modification of aramid fiber

[0013] Aramid fiber is added to ethylene dichloride and dispersed evenly, and then epichlorohydrin is added. After the addition is completed, the temperature is raised to 60-65°C, and anhydrous aluminum chloride is added. After the addition is completed, the mixture is stirred for 2-4 hours at the same temperature. The fiber material is separated, washed, and vacuum dried to obtain epoxy functionalized aramid fiber.

[0014] Step 2: Preparation of modified aramid fiber

[0015] The epoxy functionalized aramid fiber is added to N,N-dimethylformamide and dispersed evenly. Then, 1,1'-ferrocenecarboxylic acid and a catalyst are added to the formed dispersion. After the addition is completed, the mixture is stirred evenly and nitrogen is introduced for protection. The temperature is raised to 70-80°C and kept warm for 3-6 hours. Then, a chain extender is added and the temperature is further raised to 90-100°C. After continuous stirring for 9-18 hours, the temperature is lowered and the material is discharged. The fiber material is collected, washed, and vacuum dried to obtain the modified aramid fiber.

[0016] As a further embodiment of the present invention, in step 2, the catalyst is any one of tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium chloride, tetrabutylammonium chloride or tetrabutylammonium hydrogen sulfate.

[0017] As a further embodiment of the present invention, in step 2, the preparation method of the chain extender is:

[0018] Add 1,3-diglycidyl ether glycerol, 3,5-bis(trifluoromethyl)phenyldimethylsilyl chloride and 1,4-dioxane to a reactor filled with nitrogen. After the addition is completed, start stirring to form a uniform reaction liquid. Then add an acid binding agent to the reaction liquid. After the addition is completed, raise the temperature to 60-70°C, stir for 4-8 hours, evaporate to remove the solvent, cool and discharge the material to obtain a chain extender.

[0019] As a further embodiment of the present invention, the molar ratio of the 1,3-diglycidyl ether glycerol to 3,5-bis(trifluoromethyl)phenyldimethylchlorosilane is 1:1.

[0020] As a further embodiment of the present invention, the acid binding agent is triethylamine or pyridine.

[0021] As a further embodiment of the present invention, the mass ratio of the 1,1'-ferrocenecarboxylic acid, the epoxidized aramid fiber and the chain extender is 1.2-1.8:1:1.5-2.4.

[0022] In the above technical solution, epichlorohydrin is first used as a surface modification agent, and under the catalytic action of anhydrous aluminum chloride, it undergoes a Friedel-Crafts reaction with aramid fiber, thereby modifying the surface of the aramid fiber with epoxy substituents to obtain epoxy-functionalized aramid fiber. Then, 1,1'-ferrocenecarboxylic acid is used as a further modification agent, and under the action of a catalyst, the carboxyl substituents in its structure undergo a ring-opening esterification reaction with the epoxy groups of the epoxy-functionalized aramid fiber. The excess 1,1'-ferrocenecarboxylic acid in the system can undergo continuous and uninterrupted ring-opening esterification with two equivalent epoxy groups in the chain extender structure under the action of the catalyst, thereby forming an epoxy group of the epoxy-functionalized aramid fiber as an active initiation site, which triggers the ring-opening esterification polymerization of 1,1'-ferrocenecarboxylic acid and the chain extender, thereby obtaining an aramid fiber whose surface is modified with a macromolecular substance alternately linked by ferrocene and fluoromethylbenzene connected by ester bonds, i.e., a modified aramid fiber.

[0023] Among them, the chain extender is made of 1,3-diepoxyglyceryl ether glycerol and 3,5-bis(trifluoromethyl)phenyldimethylchlorosilane as raw materials. Under the action of an acid binding agent, the Si-Cl in each other's structure undergoes a substitution reaction with the hydroxyl substituent to obtain a chain extender connected by Si-O bonds and containing two equivalents of epoxy substituents in the structure.

[0024] As a further embodiment of the present invention, the preparation method of the rubber composition is as follows:

[0025] After weighing all the raw materials according to their weight, add them into an internal mixer, set the temperature to 150-160°C, and mix them for 3-5 minutes. Then, feed the formed mixture into an extruder through the feed port and perform melt extrusion granulation at a temperature of 170-180°C.

[0026] As a further embodiment of the present invention, the silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane; and the inorganic additive is any one of boron nitride, nano-silicon dioxide, graphene, carbon nanotubes or carbon black.

[0027] A preparation process for a high-elasticity, high-pressure, impact-resistant, and wear-resistant rubber carpet comprises the following steps:

[0028] The first step is to heat the rubber composition to 170-180°C to make it molten, then pour the molten material into a mold, and then use an extrusion process to extrude it to form a rubber layer;

[0029] The second step is to cover the surface of the rubber layer with non-woven fabric, and adhere the non-woven fabric to the surface of the rubber layer by means of pressure fusion to form a non-woven fabric layer;

[0030] The third step is to evenly apply acrylic pressure-sensitive adhesive on the surface of the non-woven fabric layer, and then cover the acrylic fiber on the upper surface of the pressure-sensitive adhesive, extrude and form a chemical fiber layer.

[0031] Beneficial effects of the present invention:

[0032] The present invention prepares an aramid fiber with a surface modified with a macromolecular substance of ferrocene-fluoromethylbenzene alternatingly connected by an ester bond as an additive, and adds it to the rubber layer formula of the rubber carpet. First, the macromolecular substance contained on the surface of the aramid fiber can extend to various regions of the rubber matrix during the melt extrusion process, and form a network structure that is mutually entangled with the rubber molecular chain, thereby making the aramid fiber exist in the rubber layer in the form of a physical core. This form of existence can greatly improve the interfacial performance between the aramid fiber and the rubber substrate, and thus can efficiently utilize the inherent advantages of the aramid fiber and the force conduction effect of the network structure to improve the impact resistance and wear resistance of the rubber layer. Secondly, the ferrocene and rigid benzene ring structure contained in the macromolecular substance structure and the silicon-oxygen bond generated by the substitution reaction can all have a positive effect on the high temperature resistance of the rubber layer, improving the thermal aging problem caused by the long-term application of the rubber carpet on the floor heating floor. In addition, the macromolecular substance structure also contains a large amount of fluorine elements and silicon-oxygen bonds. These groups have extremely low surface energy, which can make the rubber layer produce a super-hydrophobic surface, thereby giving the rubber carpet a good self-cleaning effect.

[0033] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. DETAILED DESCRIPTION

[0034] The following will be combined with the embodiments to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0035] Preparation Example

[0036] Preparation of modified aramid fiber:

[0037] Step 1: Functionalization modification of aramid fiber

[0038] 3.5 g of aramid fiber with a length of 1 mm was added to dichloroethane and uniformly dispersed. Then, 1.6 g of epichlorohydrin was added. After the addition was completed, the temperature was raised to 60°C and 0.2 g of anhydrous aluminum chloride was added. After the addition was completed, the mixture was stirred for 3 hours at this temperature. The fiber material was separated, washed, and vacuum-dried to obtain epoxy-functionalized aramid fiber.

[0039] Referring to the standard GB / T 1677-2008, the hydrochloric acid-acetone titration test method was used, and 0.5g of epoxy-functionalized aramid fiber was taken as the titration sample for epoxy value testing. The results showed that the epoxy value of the sample was 3.157mmol / g. This is due to the Friedel-Crafts reaction between epichlorohydrin and aramid fiber, which introduces epoxy groups onto the surface of the aramid fiber.

[0040] Step 2: Preparation of chain extender

[0041] Add 0.2 g of 1,3-diglycidyl ether glycerol, 0.3 g of 3,5-bis(trifluoromethyl)phenyldimethylsilyl chloride, and 1,4-dioxane to a reactor filled with nitrogen. After the addition is complete, stir and wait until a uniform reaction liquid is formed. Then, add 0.05 g of triethylamine to the reaction liquid. After the addition is complete, raise the temperature to 65°C, stir for 6 hours, evaporate the solvent, cool and discharge the material, and the chain extender can be obtained.

[0042] Step 3: Preparation of modified aramid fiber

[0043] 1.2 g of epoxy functionalized aramid fiber was added to N,N-dimethylformamide and dispersed evenly. Then, 2.1 g of 1,1'-ferrocenecarboxylic acid and 0.1 g of tetrabutylammonium bromide were added to the formed dispersion. After the addition was completed, the mixture was stirred evenly and nitrogen was introduced for protection. The temperature was raised to 75°C and kept warm for 4 hours. Then, 2 g of chain extender was added and the temperature was further raised to 95°C. After continuous stirring for 16 hours, the mixture was cooled and discharged. The fiber material was collected, washed, and vacuum dried to obtain the modified aramid fiber.

[0044] Using the same titration test method, 0.5g of modified aramid fiber was taken as the titration test sample for epoxy value test. The results showed that the epoxy value was 0.281mmol / g. This was due to the ring-opening esterification reaction between the epoxy groups of the aramid fiber and 1,1'-ferrocenecarboxylic acid, resulting in a large amount of consumption.

[0045] Example 1

[0046] Preparation of rubber composition

[0047] According to parts by weight, 60 parts of chloroprene rubber, 50 parts of styrene-butadiene rubber, 40 parts of natural rubber, 25 parts of thermoplastic polyurethane elastomer, 10 parts of ethylene-vinyl acetate copolymer, 3 parts of modified aramid fiber, 0.1 part of benzoyl peroxide, 50 parts of white oil, 4 parts of 3-(methacryloyloxy)propyltrimethoxysilane and 5 parts of boron nitride were added to an internal mixer, the temperature was set to 150°C, and the internal mixing was carried out for 5 minutes. Then, the formed mixture was fed into the extruder through the feed port and melt-extruded and granulated at a temperature of 170°C.

[0048] The preparation method of the modified aramid fiber is shown in the preparation example, and the same applies to the following.

[0049] Example 2

[0050] Preparation of rubber composition

[0051] According to parts by weight, 62 parts of chloroprene rubber, 55 parts of styrene-butadiene rubber, 45 parts of natural rubber, 28 parts of thermoplastic polyurethane elastomer, 12 parts of ethylene-vinyl acetate copolymer, 5 parts of modified aramid fiber, 0.2 parts of benzoyl peroxide, 60 parts of white oil, 6 parts of 3-(methacryloyloxy)propyltrimethoxysilane and 8 parts of nano-silica were added to an internal mixer, the temperature was set to 160°C, and the internal mixing was carried out for 4 minutes. Then, the formed mixture was fed into the extruder through the feed port and melt-extruded and granulated at a temperature of 180°C.

[0052] Example 3

[0053] Preparation of rubber composition

[0054] According to parts by weight, 70 parts of chloroprene rubber, 60 parts of styrene-butadiene rubber, 50 parts of natural rubber, 35 parts of thermoplastic polyurethane elastomer, 20 parts of ethylene-vinyl acetate copolymer, 6 parts of modified aramid fiber, 0.3 parts of benzoyl peroxide, 70 parts of white oil, 8 parts of 3-(methacryloyloxy)propyltrimethoxysilane and 10 parts of carbon black were added to an internal mixer, the temperature was set to 160°C, and the internal mixing was carried out for 4 minutes. Then, the formed mixture was fed into the extruder through the feed port and melt-extruded and granulated at a temperature of 180°C.

[0055] Comparative Example 1

[0056] Preparation of rubber composition

[0057] According to parts by weight, 62 parts of chloroprene rubber, 55 parts of styrene-butadiene rubber, 45 parts of natural rubber, 28 parts of thermoplastic polyurethane elastomer, 12 parts of ethylene-vinyl acetate copolymer, 5 parts of aramid fiber, 0.2 parts of benzoyl peroxide, 60 parts of white oil, 6 parts of 3-(methacryloyloxy)propyltrimethoxysilane and 8 parts of nano-silica were added to an internal mixer, the temperature was set to 160°C, and the internal mixing was carried out for 4 minutes. Then, the formed mixture was fed into the extruder through the feed port and melt-extruded and granulated at a temperature of 180°C.

[0058] Comparative Example 2

[0059] Preparation of rubber composition

[0060] According to parts by weight, 62 parts of chloroprene rubber, 55 parts of styrene-butadiene rubber, 45 parts of natural rubber, 28 parts of thermoplastic polyurethane elastomer, 12 parts of ethylene-vinyl acetate copolymer, 0.2 parts of benzoyl peroxide, 60 parts of white oil, 6 parts of 3-(methacryloyloxy)propyltrimethoxysilane and 8 parts of nano-silica were added to an internal mixer, the temperature was set to 160°C, and the internal mixing was carried out for 4 minutes. Then, the formed mixture was fed into the extruder through the feed port and melt-extruded and granulated at a temperature of 180°C.

[0061] Performance Testing

[0062] The rubber compositions in the examples and comparative examples were subjected to various performance tests, and the results are recorded in the following table:

[0063] Table 1 - Test results

[0064] <![CDATA[Impact strength / kJ / m 2 > <![CDATA[Wear volume / cm 3 > Phenomenon Water contact angle / ° Example 1 25.4 0.281 No obvious phenomenon 150 Example 2 25.7 0.276 No obvious phenomenon 151 Example 3 25.6 0.278 No obvious phenomenon 150 Comparative Example 1 21.1 0.315 Cracking and chalking 127 Comparative Example 2 16.9 0.383 Cracking and chalking 127

[0065] The impact strength is tested according to the standard GB / T 1843-2008;

[0066] Wear resistance is tested in accordance with GB / T 1689-2014;

[0067] The high temperature resistance test method is as follows: a rubber composition with a size of 5cm×5cm×4mm is placed in an oven at 80°C, taken out after 48 hours, and the sample phenomenon is observed to evaluate the high temperature resistance;

[0068] The water contact angle was directly measured using a water contact angle meter.

[0069] The analysis and test results show that the rubber composition prepared by using modified aramid fiber as an additive has obviously better comprehensive performance.

[0070] When unmodified aramid fiber is used to replace modified aramid fiber, due to the interface problem between it and the rubber substrate, it cannot be evenly dispersed, so the strength and wear resistance are significantly reduced. Moreover, since it does not contain macromolecular substances, other properties are significantly negatively affected.

[0071] A high-elasticity, high-pressure, impact-resistant, and wear-resistant rubber carpet is prepared using the rubber composition of the embodiment of the present invention. The specific preparation process includes the following steps:

[0072] The first step is to heat the rubber composition to 170°C to make it molten, then pour the molten material into a mold, and then use an extrusion process to extrude it to form a rubber layer;

[0073] The second step is to cover the surface of the rubber layer with non-woven fabric, and adhere the non-woven fabric to the surface of the rubber layer by means of pressure fusion to form a non-woven fabric layer;

[0074] Step 3: Evenly coat the surface of the non-woven fabric layer with acrylic pressure-sensitive adhesive, controlling the coating amount to 200g / m 2 , then cover the acrylic fiber on the upper surface of the pressure-sensitive adhesive, extrude and shape it to form a chemical fiber layer.

[0075] Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enable any technician in the field to practice the present invention, including making and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principles of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the literal description of the claims, or if they include equivalent structural elements that are not substantially different from the literal description of the claims, then these other embodiments should also be included in the scope of the claims.

[0076] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A high-elasticity, high-pressure, impact-resistant, wear-resistant rubber carpet, characterized in that: From top to bottom, it includes a chemical fiber layer, a non-woven fabric layer and a rubber layer; The rubber layer is made by melting the rubber composition and then extruding it; The rubber composition includes the following components measured in parts by weight: 60-70 parts of chloroprene rubber, 50-60 parts of styrene-butadiene rubber, 40-50 parts of natural rubber, 25-35 parts of thermoplastic polyurethane elastomer, 10-20 parts of ethylene-vinyl acetate copolymer, 3-6 parts of modified aramid fiber, 0.1-0.3 parts of benzoyl peroxide, 50-70 parts of white oil, 4-8 parts of silane coupling agent, and 5-10 parts of inorganic additives.

2. The high-elasticity, high-pressure, impact-resistant, wear-resistant rubber carpet according to claim 1, characterized in that: The preparation method of the modified aramid fiber comprises the following steps: Step 1: Functionalization modification of aramid fiber Using epichlorohydrin as a modifier, the surface of aramid fiber was grafted and modified under the catalysis of anhydrous aluminum chloride to obtain epoxy functionalized aramid fiber. Step 2: Preparation of modified aramid fiber Using 1,1'-ferrocenecarboxylic acid as a linker, the epoxidized aramid fiber was firstly further modified under the action of a catalyst, and then a chain extender was added to carry out in-situ polymerization on the surface of the aramid fiber to obtain the modified aramid fiber.

3. The high-elasticity, high-pressure, impact-resistant, wear-resistant rubber carpet according to claim 2, characterized in that: In step 2, the catalyst is any one of tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium chloride, tetrabutylammonium chloride or tetrabutylammonium hydrogen sulfate.

4. The high-elasticity, high-pressure, impact-resistant, wear-resistant rubber carpet according to claim 2, characterized in that: In step 2, the chain extender is prepared by using 1,3-diglycidyl ether glycerol and 3,5-bis(trifluoromethyl)phenyldimethylchlorosilane as raw materials, and performing substitution under the action of an acid binding agent to obtain the chain extender.

5. The high-elasticity, high-pressure, impact-resistant, wear-resistant rubber carpet according to claim 4, characterized in that: The molar ratio of the 1,3-diglycidyl ether glycerol to 3,5-bis(trifluoromethyl)phenyldimethylchlorosilane is 1:

1.

6. The high-elasticity, high-pressure, impact-resistant, wear-resistant rubber carpet according to claim 4, characterized in that: The acid binding agent is triethylamine or pyridine.

7. The high-elasticity, high-pressure, impact-resistant, wear-resistant rubber carpet according to claim 2, characterized in that: The mass ratio of the 1,1'-ferrocenylcarboxylic acid, the epoxidized aramid fiber and the chain extender is 1.2-1.8:1:1.5-2.

4.

8. The high-elasticity, high-pressure, impact-resistant, wear-resistant rubber carpet according to claim 1, characterized in that: The preparation method of the rubber composition is as follows: After weighing all the raw materials according to their weight, add them into an internal mixer, set the temperature to 150-160°C, and mix them for 3-5 minutes. Then, feed the formed mixture into an extruder through the feed port and perform melt extrusion granulation at a temperature of 170-180°C.

9. The high-elasticity, high-pressure, impact-resistant, wear-resistant rubber carpet according to claim 1, characterized in that: The silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane; and the inorganic additive is any one of boron nitride, nano-silicon dioxide, graphene, carbon nanotubes or carbon black.

10. A process for preparing the high-elasticity, high-pressure, impact-resistant, wear-resistant rubber carpet according to claim 1, characterized in that: The following steps are involved: The first step is to heat the rubber composition to 170-180°C to make it molten, then pour the molten material into a mold, and then use an extrusion process to extrude it to form a rubber layer; The second step is to cover the surface of the rubber layer with non-woven fabric, and adhere the non-woven fabric to the surface of the rubber layer by means of pressure fusion to form a non-woven fabric layer; The third step is to evenly apply acrylic pressure-sensitive adhesive on the surface of the non-woven fabric layer, and then cover the acrylic fiber on the upper surface of the pressure-sensitive adhesive, extrude and form a chemical fiber layer.