Activating agent for polyester industrial yarn and preparation method thereof

Abstract

The invention discloses an activating agent for polyester industrial yarn and a preparation method of the activating agent. The activating agent is prepared from the following components in parts by mass: 10 parts of deionized water, 1 to 6 parts of waterborne epoxy resin, 2 to 10 parts of blocked isocyanate, 5 to 300 parts of wetting penetrant and 5 to 200 parts of epoxy curing agent. According to the activating agent for the polyester industrial yarn and the preparation method of the activating agent, the use of organic solvents can be greatly reduced, the harm to the environment and staff is reduced, and the production cost is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical solvents and relates to an activator, in particular to an activator for polyester industrial yarn and a preparation method thereof. Background Art

[0002] The fiber skeleton material in rubber products mainly plays the role of bearing load and maintaining the dimensional stability of the products. Its adhesion performance with rubber plays a decisive role in the performance and service life of rubber products.

[0003] For polyester skeleton materials, since polyester fibers and rubber matrices have large differences in polarity and rigidity, it is necessary to manufacture a dipping layer through dipping treatment to improve the bonding force of the two-phase interface. In industry, a two-bath method is generally used for dipping, that is, epoxy-isocyanate is used as the first bath, and RFL is used as the second bath. The above RFL dipping system has disadvantages. First, the two-pass dipping and drying operations increase the process and energy consumption, weakening the cost competitiveness of PET compared to other materials such as nylon. At present, when producing pre-activated yarns, major industrial yarn manufacturers mainly add activators to polyester yarns through oiling nozzles after the last pair of rollers and before winding, and then heat treat them at 65°C in a separately built drying room for 2-3 days to complete the production of pre-activated yarns; there are also manufacturers who modify the equipment, add oiling nozzles before the last pair of rollers to add activators to the yarns, and heat treat the yarns at the temperature given by the last pair of rollers to complete the production of pre-activated yarns.

[0004] Usually, the "activator" is composed of non-ionic polyethylene glycol, crown ether, epoxy compound (polymer) mixture and propylene glycol solvent. The above pre-activated yarn production methods all have disadvantages: (1) Due to the use of a large amount of organic solvents such as ethers and propylene glycol, these solvents do not participate in the reaction but only play a dilution role. They will be continuously released into the environment during the production process, which will cause waste of resources on the one hand and cause great harm to the environment and spinning workers on the other hand. (2) The pre-activated yarn currently sold on the market can only be used in products such as hoses, conveyor belts, canvas, etc., and there is insufficient adhesion when used in tire cord fabrics.

[0005] In view of this, there is an urgent need to design a new activator to overcome at least part of the above-mentioned defects of the existing activators. Summary of the invention

[0006] The invention provides an activator for polyester industrial yarn and a preparation method thereof, which can greatly reduce the use of organic solvents, reduce damage to the environment and employees and reduce production costs.

[0007] To solve the above technical problem, according to one aspect of the present invention, the following technical solution is adopted:

[0008] An activator for polyester industrial yarns, comprising: 10 parts by mass of deionized water, 1-6 parts by mass of waterborne epoxy resin, 2-10 parts by mass of blocked isocyanate, 5-300 parts by mass of a wetting and penetrating agent, and 5-200 parts by mass of an epoxy curing agent.

[0009] As an embodiment of the present invention, the waterborne epoxy resin includes polyol glycidyl ether; the polyol glycidyl ether includes at least one of glycerol glycidyl ether, polyglycerol glycidyl ether, sorbitol glycidyl ether, pentaerythritol glycidyl ether, and castor oil glycidyl ether.

[0010] As an embodiment of the present invention, the water-based epoxy resin includes at least one of EX614B, EX512, JF313, JF512, and G1701.

[0011] As an embodiment of the present invention, the blocked isocyanate includes isocyanate and a blocking agent; the blocking agent includes at least one of lutidine, caprolactam, oxadiazine ring, phenol, butanone oxime, diethylpropylamine or diethylmalonic acid.

[0012] As an embodiment of the present invention, the blocked isocyanate includes at least one of toluene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate.

[0013] As an embodiment of the present invention, the wetting and penetrating agent includes at least one of acetylenic diols, HY-1000 low-foaming wetting and penetrating agent, and BYK wetting and dispersing agent.

[0014] According to another aspect of the present invention, the following technical scheme is adopted: a method for preparing the above-mentioned activator, the preparation method comprising:

[0015] Step S1, adding 10 parts by weight of deionized water into a reaction container, adding 1-6 parts by weight of a water-soluble epoxy resin into the reaction container, and stirring for a first set time;

[0016] Step S2, adding 2-10 parts by weight of blocked isocyanate into the reaction container, and stirring for a second set time;

[0017] Step S3, adding 5-300 parts by weight of a wetting and penetrating agent into the reaction container, and stirring for a third set time;

[0018] Step S4, adding 5-200 parts by weight of a room temperature epoxy curing agent into the reaction container, and stirring for a fourth set time to obtain a water-based activator.

[0019] As an embodiment of the present invention, in step S1, the yarn is sequentially subjected to the unheated GR1 roller, the GR2 roller at 90-100°C, the GR3 roller at 120-140°C, the GR4 roller at 235-250°C and the unheated GR5 roller;

[0020] In step S2, before winding, the prepared water-based activator is applied to the yarn at the oil nozzle to complete the winding and obtain the wound yarn;

[0021] In step S3, the wound yarn is not subjected to heat treatment and is placed at room temperature for at least 1 week to obtain polyester activated yarn;

[0022] In step S4, the polyester activated yarn is twisted, woven, and dipped in glue according to the product specification.

[0023] As an embodiment of the present invention, the conditions for the dipping treatment are: drying oven H1 temperature 140-170°C, stretching tension 500-2000daN, stretching oven H2 temperature 230-250°C, tension 1000-4000daN, shaping oven H3 temperature 230-250°C, tension 300-1000daN, speed 65-95 m / min.

[0024] The beneficial effects of the present invention are as follows: the activator for polyester industrial yarn and the preparation method thereof proposed in the present invention can greatly reduce the use of organic solvents, reduce damage to the environment and employees, and reduce production costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The present invention is a flowchart of a method for preparing an activator for polyester industrial yarn in one embodiment of the present invention. DETAILED DESCRIPTION

[0026] The preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0027] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0028] The description in this section is only for several typical embodiments, and the present invention is not limited to the scope of the embodiments. The same or similar prior art means and some technical features in the embodiments are mutually replaced within the scope of the present invention.

[0029] Unless otherwise indicated, implied from the context, or customary in the prior art, all parts and percentages in this application are based on weight, and the test and characterization methods used are all current as of the filing date of this application. Where applicable, the contents of any patent, patent application or publication referred to in this application are fully incorporated herein by reference, and their equivalent patent families are also incorporated by reference, especially the definitions of synthesis techniques, product and processing designs, polymers, comonomers, initiators or catalysts disclosed in these documents in the art. If the definition of a specific term disclosed in the prior art is inconsistent with any definition provided in this application, the definition of the term provided in this application shall prevail.

[0030] Numerical ranges in this application are approximate values, so unless otherwise specified, they may include numerical values ​​outside the range. Numerical ranges include all numerical values ​​from the lower limit to the upper limit increased by 1 unit, provided that there is an interval of at least 2 units between any lower value and any higher value. For example, if the recorded component, physical or other properties (such as molecular weight, melt index, etc.) are 100 to 1000, it means that all single values ​​are clearly listed, such as 100, 101, 102, etc., and all sub-ranges, such as 100 to 166, 155 to 170, 198 to 200, etc. For a range containing a numerical value less than 1 or containing a fraction greater than 1 (such as 1.1, 1.5, etc.), 1 unit is appropriately regarded as 0.0001, 0.001, 0.01 or 0.1. For a range containing a single digit less than 10 (such as 1 to 5), 1 unit is usually regarded as 0.1. These are only specific examples of what is intended to be expressed, and all possible combinations of values ​​between the lowest and highest values ​​listed are considered to be clearly recorded in this application. It should also be noted that the terms "first", "second", etc. in this article do not limit the order of precedence, but are only used to distinguish substances with different structures.

[0031] When used with respect to chemical compounds, unless expressly specified otherwise, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively). In addition, nouns using "a," "an," or "the" also include their plural forms unless expressly specified otherwise.

[0032] The terms "comprising", "including", "having" and their derivatives do not exclude the presence of any other components, steps or processes, and are irrelevant to whether these other components, steps or processes are disclosed in this application. To eliminate any doubt, unless explicitly stated, all compositions using the terms "comprising", "including", or "having" in this application may include any additional additives, adjuvants or compounds. On the contrary, except for those necessary for operating performance, the term "essentially consisting of..." excludes any other components, steps or processes from the scope of any description of the term below. The term "consisting of..." does not include any components, steps or processes that are not specifically described or listed. Unless explicitly stated, the term "or" refers to the listed individual members or any combination thereof.

[0033] The description of the steps in each embodiment in the specification is only for the convenience of explanation, and the implementation method of the present application is not limited by the order of implementation of the steps.

[0034] The invention discloses an activator for polyester industrial yarn, wherein the activator comprises: 10 parts by weight of deionized water, 1-6 parts by weight of water-based epoxy resin, 2-10 parts by weight of blocked isocyanate, 5-300 parts by weight of wetting and penetrating agent, and 5-200 parts by weight of epoxy curing agent (e.g., room temperature epoxy curing agent).

[0035] In one embodiment of the present invention, the waterborne epoxy resin includes polyol glycidyl ether; the polyol glycidyl ether includes at least one of glycerol glycidyl ether, polyglycerol glycidyl ether, sorbitol glycidyl ether, pentaerythritol glycidyl ether, and castor oil glycidyl ether.

[0036] The waterborne epoxy resin includes at least one of EX614B, EX512, JF313, JF512, and G1701.

[0037] The blocked isocyanate includes isocyanate and a blocking agent; the blocking agent includes at least one of dimethyl pyridine, caprolactam, oxadiazine ring, phenol, butanone oxime, diethylpropylamine or diethylmalonic acid. The blocked isocyanate includes at least one of toluene diisocyanate, diphenylmethane diisocyanate and 1,6-hexamethylene diisocyanate. The wetting and penetrating agent includes at least one of acetylenic diols, HY-1000 low foaming wetting and penetrating agent and BYK wetting and dispersing agent.

[0038] The present invention further discloses a method for preparing the above activator. Figure 1 FIG. 1 is a flow chart of a method for preparing an activating agent for polyester industrial yarn according to an embodiment of the present invention; Figure 1 , the preparation method comprises:

[0039] [Step S1] Add 10 parts by mass of deionized water to a reaction container, add 1-6 parts by mass of a water-soluble epoxy resin to the reaction container, and stir for a first set time;

[0040] [Step S2] Add 2-10 parts by weight of blocked isocyanate to the reaction container and stir for a second set time;

[0041] [Step S3] Add 5-300 parts by mass of a wetting and penetrating agent to the reaction container, and stir for a third set time;

[0042] [Step S4] Add 5-200 parts by mass of a room temperature epoxy curing agent into the reaction container and stir for a fourth set time to obtain a water-based activator.

[0043] In one embodiment of the present invention, in step S1, the yarn is sequentially subjected to the unheated GR1 roller, the GR2 roller at 90-100°C, the GR3 roller at 120-140°C, the GR4 roller at 235-250°C and the unheated GR5 roller;

[0044] In step S2, before winding, the prepared water-based activator is applied to the yarn at the oil nozzle to complete the winding and obtain the wound yarn;

[0045] In step S3, the wound yarn is not subjected to heat treatment and is placed at room temperature for at least 1 week to obtain polyester activated yarn;

[0046] In step S4, the polyester activated yarn is twisted, woven, and dipped in glue according to the product specification.

[0047] The conditions for the dipping treatment are: drying oven H1 temperature 140-170°C, stretching tension 500-2000daN, stretching oven H2 temperature 230-250°C, tension 1000-4000daN, shaping oven H3 temperature 230-250°C, tension 300-1000daN, speed 65-95 m / min.

[0048] In the embodiments of the present invention, there is no particular limitation on the source of the blocked isocyanate, and commercially available blocked isocyanates known to those skilled in the art may be used, such as caprolactam-blocked isocyanate IL-6 (EMS Chemical Group).

[0049] The source of the waterborne epoxy resin in the embodiment of the present invention is not particularly limited, and commercially available products known in the art may be used, such as G1701 (EMS Chemical Group), EX614B (NAGASE), or EX512 (NAGASE).

[0050] Example 1

[0051] In this embodiment, the preparation method of the water-based activator includes: adding 10 kg of deionized water to a reaction tank, then adding 2 kg of water-soluble epoxy resin G1701, stirring for 0.5-1.5 hours, then adding 3 kg of blocked isocyanate I L06, stirring for 10-30 minutes, continuing to add 50 g of wetting and penetrating agent acetylene glycol surfactant ZY-1104, stirring for 10-20 minutes, and continuing to add 20 g of room temperature epoxy curing agent triethylene diamine, stirring for 5 minutes to obtain the water-based activator;

[0052] Example 2

[0053] In this embodiment, the preparation method of the water-based activator includes: adding 10 kg of deionized water to a reaction tank, then adding 2 kg of water-soluble epoxy resin G1701, stirring for 0.5-1.5 hours, then adding 2 kg of blocked isocyanate I L06, stirring for 10-30 minutes, continuing to add 50 g of wetting and penetrating agent acetylene glycol surfactant ZY-1104, stirring for 10-20 minutes, and continuing to add 150 g of room temperature epoxy curing agent triethylene diamine, stirring for 5 minutes to obtain the water-based activator;

[0054] Example 3

[0055] In this embodiment, the preparation method of the water-based activator includes: adding 10 kg of deionized water to a reaction tank, then adding 2 kg of water-soluble epoxy resin G1701, stirring for 0.5-1.5 hours, then adding 5 kg of blocked isocyanate IL06, stirring for 10-30 minutes, continuing to add 50 g of wetting and penetrating agent acetylene glycol surfactant ZY-1104, stirring for 10-20 minutes, and continuing to add 150 g of room temperature epoxy curing agent triethylene diamine, stirring for 5 minutes to obtain the water-based activator;

[0056] Example 4

[0057] In this embodiment, the preparation method of the water-based activator includes: adding 10 kg of deionized water to a reaction tank, then adding 1 kg of water-soluble epoxy resin G1701 and 1 kg of water-soluble epoxy resin EX614B, stirring for 0.5-1.5 hours, then adding 5 kg of blocked isocyanate IL06, stirring for 10-30 minutes, continuing to add 50 g of wetting and penetrating agent acetylene glycol surfactant ZY-1104, stirring for 10-20 minutes, and continuing to add 150 g of room temperature epoxy curing agent triethylene diamine, stirring for 5 minutes to obtain the water-based activator.

[0058] Example 5

[0059] In this embodiment, the preparation method of the water-based activator includes: adding 10 kg of deionized water to a reaction tank, then adding 2 kg of water-soluble epoxy resin EX614B, stirring for 0.5-1.5 hours, then adding 5 kg of blocked isocyanate IL06, stirring for 10-30 minutes, continuing to add 50 g of wetting and penetrating agent acetylene glycol surfactant ZY-1104, stirring for 10-20 minutes, and continuing to add 150 g of room temperature epoxy curing agent triethylene diamine, stirring for 5 minutes to obtain the water-based activator.

[0060] The conditions for the dipping treatment are: drying oven H1 temperature 140-170°C, drawing tension 500-2000daN, drawing oven H2 temperature 230-250°C, tension 1000-4000daN, shaping oven H3 temperature 230-250°C, tension 300-1000daN, speed 65-95 m / min

[0061] Comparative Example 1

[0062] The activated silk was produced using German Zschimmer & Schwarz chemical activator TC12, with heat treatment at 80°C*48h.

[0063] Comparative Example 2

[0064] Polyester cord produced by conventional two-bath process without using activator.

[0065] The present invention takes 1500D / 2 polyester cord fabric as an example. In Examples 1-5 and Comparative Example 1, the yarns are sequentially subjected to the unheated GR1 roller, the GR2 roller at 90°C, the GR3 roller at 140°C, the GR4 roller at 245°C and the unheated GR5 roller. Before winding, the configured activator is applied to the yarn at the oil nozzle to complete the winding and obtain the completed activated yarn; the completed yarn is not heat-treated and placed at room temperature for at least 1 week. The yarn of Comparative Example 1 is heat-treated at 80°C for 48h to obtain polyester activated yarn. The polyester activated cord fabrics of Examples 1-5 and Comparative Example 1 are dipped in RFL one bath. The conditions for the one-bath dipping treatment are: drying temperature 165°C, tension 800daN, drawing temperature 235°C, tension 2000daN, setting temperature 235°C, tension 500daN and speed 75 m / min; Comparative Example 2 adopts the conventional two-bath dipping method. The conditions of the two-bath dipping treatment are: drying temperature 165°C, tension 800daN, drawing temperature 235°C, tension 2000daN, drying temperature 165°C, tension 800daN, setting temperature 235°C, tension 500daN, speed 75 m / min; the polyester cord after dipping treatment was tested, and the test results are shown in Table 1:

[0066] Table 1 Physical property data comparison table

[0067]

[0068] The polyester cords after the dip treatment of the above-mentioned Examples 1-5 and Comparative Examples 1-2 were subjected to adhesion test (CRA and H extraction), and the standard glue was completely coated on the dipped cord to prepare the CRA style, which was placed on a flat vulcanizer for vulcanization treatment, with a vulcanization temperature of 160°C, a vulcanization pressure of 3.5MPa, and a vulcanization time of 20min and 60min respectively. Surface grade: A: Surface coating range: 96-100%; B: Surface coating range: 71-95%; C: Surface coating range: 41-70%; D: Surface coating range: 11-40%; E: Surface coating range: 0-10%; The test results are as shown in Table 2:

[0069] Table 2 Adhesion data comparison table

[0070]

[0071] From the data in Table 2, it can be seen that compared with Comparative Example 1, the bonding force of Examples 1-5 is significantly higher than that of the competitor TC12 after heat aging, indicating that the water-based activator has reached the existing level and can be used as a substitute for hoses, conveyor belts, and canvas. Compared with Comparative Example 2, the bonding force of Examples 4-5 has reached and exceeded the level of the existing two-bath method. Compared with the two-bath method, at least one drying oven is saved in the dipping stage, which can reduce energy consumption and save production costs.

[0072] In summary, the activator for polyester industrial yarn and the preparation method thereof proposed in the present invention can greatly reduce the use of organic solvents, reduce damage to the environment and employees, and reduce production costs.

[0073] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0074] The description and application of the present invention here are illustrative, and it is not intended to limit the scope of the present invention to the above-mentioned embodiments. The effects or advantages involved in the embodiments may not be embodied in the embodiments due to interference from various factors, and the description of the effects or advantages is not used to limit the embodiments. The deformation and change of the embodiments disclosed here are possible, and the replacement of the embodiments and the various equivalent parts are well known to those of ordinary skill in the art. It should be clear to those skilled in the art that the present invention can be implemented in other forms, structures, arrangements, proportions, and with other components, materials and parts without departing from the spirit or essential features of the present invention. Other deformations and changes can be made to the embodiments disclosed here without departing from the scope and spirit of the present invention.

Claims

1. An activator for polyester industrial yarn, characterized in that: The activator comprises: 10 parts by mass of deionized water, 1-6 parts by mass of waterborne epoxy resin, 2-10 parts by mass of blocked isocyanate, 5-300 parts by mass of wetting and penetrating agent, and 5-200 parts by mass of epoxy curing agent.

2. The activator for polyester industrial yarn according to claim 1, characterized in that: The waterborne epoxy resin includes polyol glycidyl ether; the polyol glycidyl ether includes at least one of glycerol glycidyl ether, polyglycerol glycidyl ether, sorbitol glycidyl ether, pentaerythritol glycidyl ether and castor oil glycidyl ether.

3. The activator for polyester industrial yarn according to claim 1, characterized in that: The waterborne epoxy resin includes at least one of EX614B, EX512, JF313, JF512, and G1701.

4. The activator for polyester industrial yarn according to claim 1, characterized in that: The blocked isocyanate comprises isocyanate and a blocking agent; the blocking agent comprises at least one of dimethylpyridine, caprolactam, oxadiazine ring, phenol, butanone oxime, diethylpropylamine or diethylmalonic acid.

5. The activator for polyester industrial yarn according to claim 1, characterized in that: The blocked isocyanate includes at least one of toluene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate.

6. The activator for polyester industrial yarn according to claim 1, characterized in that: The wetting and penetrating agent includes at least one of acetylenic diols, HY-1000 low-foaming wetting and penetrating agent, and BYK wetting and dispersing agent.

7. A method for preparing the activator according to any one of claims 1 to 6, characterized in that: The preparation method comprises: Step S1, adding 10 parts by mass of deionized water into a reaction container, adding 1-6 parts by mass of a water-soluble epoxy resin into the reaction container, and stirring for a first set time; Step S2, adding 2-10 parts by weight of blocked isocyanate into the reaction container, and stirring for a second set time; Step S3, adding 5-300 parts by weight of a wetting and penetrating agent into the reaction container, and stirring for a third set time; Step S4, adding 5-200 parts by weight of a room temperature epoxy curing agent into the reaction container, and stirring for a fourth set time to obtain a water-based activator.

8. The preparation method according to claim 7, characterized in that: In step S1, the yarn is sequentially passed through the unheated GR1 roller, the GR2 roller at 90-100°C, the GR3 roller at 120-140°C, the GR4 roller at 235-250°C and the unheated GR5 roller; In step S2, before winding, the prepared water-based activator is applied to the yarn at the oil nozzle to complete the winding and obtain the wound yarn; In step S3, the wound yarn is not subjected to heat treatment and is placed at room temperature for at least 1 week to obtain polyester activated yarn; In step S4, the polyester activated yarn is twisted, woven, and dipped in glue according to the product specification.

9. The preparation method according to claim 7, characterized in that: In step S4, the conditions for the dipping treatment are: drying oven H1 temperature 140-170°C, stretching tension 500-2000daN, stretching oven H2 temperature 230-250°C, tension 1000-4000daN, shaping oven H3 temperature 230-250°C, tension 300-1000daN, speed 65-95 m / min.

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