CN118994728A

CN118994728A - Processing aid for anti-blooming rubber and preparation method thereof

Info

Publication number: CN118994728A
Application number: CN202411318279.8A
Authority: CN
Inventors: 佟峰; 邹豫; 林怡彤; 梁子铭
Original assignee: Guangxi Donglan New Material Co ltd
Current assignee: Guangxi Donglan New Material Co ltd
Priority date: 2024-09-20
Filing date: 2024-09-20
Publication date: 2024-11-22

Abstract

The invention discloses a processing aid for anti-blooming rubber and a preparation method thereof, belonging to the technical field of rubber aids, wherein the processing aid comprises 40-50 parts of di-tert-butyl isopropyl peroxide, 40-45 parts of calcium carbonate, 5-15 parts of other inorganic inert materials and 5-10 parts of anti-blooming aid according to weight percentage; the anti-frosting auxiliary agent is prepared from amino-terminated hyperbranched polyamide and unsaturated glycidyl ester through an epoxy ring-opening reaction. The processing aid for the anti-blooming rubber solves the problem that blooming is easy to occur when BIPB is added into a rubber material. The processing auxiliary agent comprises a self-made anti-frosting auxiliary agent, is obtained by epoxy ring-opening reaction of amino-terminated hyperbranched polyamide and unsaturated glycidyl ester, has good dispersion performance and adsorption performance, and can inhibit the problem that rubber materials are easy to frost.

Description

Processing aid for anti-blooming rubber and preparation method thereof

Technical Field

The invention belongs to the technical field of rubber additives, and particularly relates to a processing additive for anti-frosting rubber and a preparation method thereof.

Background

Rubber bloom includes both gum appearance bloom and product appearance bloom, wherein the bloom is a phenomenon that a liquid or solid compounding agent migrates from the interior of rubber to the surface of rubber, and the reason for the bloom is mainly caused by supersaturation of the compounding agent in the gum or some incompatible compounds with smaller molecular weight.

Di-tert-butylperoxyisopropyl benzene, commonly known as B IPB or "odorless DCP". The crosslinking agent has the advantages that the crosslinking efficiency of the B IPB is higher due to the difunctional groups and the high active oxygen content, the addition amount of the crosslinking agent is about 2/3 of that of the common DCP (dicumyl peroxide) under the condition of the same crosslinking effect, and the odor of the crosslinking agent is small in the operation process and the prepared products, and the crosslinking agent is commonly used as the crosslinking agent of plastics and rubber such as chlorinated polyethylene, ethylene propylene diene monomer, ethylene-vinyl acetate copolymer, silicone rubber, nitrile rubber and the like. The main disadvantage of B IPB is that it is easy to cause the problem of frosting of the product, the reason for frosting is mainly that the decomposition product of B IPB, namely dihydroxyl-1, 4-diisopropylbenzene, has smaller solubility in part of rubber, and the frosting formed is mostly white or dark white needle-like crystals.

The surface frosting of rubber can affect the appearance quality and decorative performance of rubber, and the frosting can reduce the surface viscosity of the rubber material during calendaring, thereby causing scorching of the rubber material and aging of products. The frosting of the rubber products not only seriously affects the appearance quality of the products, but also affects the service performance and service life of the rubber products to a certain extent, and also affects the technological performance and physical and mechanical properties of the sizing materials.

Disclosure of Invention

The invention aims to provide a processing aid for anti-frosting rubber and a preparation method thereof, which are used for solving the problem that frosting is easy to occur when BIPB is added into rubber materials.

The aim of the invention can be achieved by the following technical scheme:

The processing aid for the anti-blooming rubber comprises 40-50 parts of di-tert-butyl isopropyl peroxide, 40-45 parts of calcium carbonate, 5-15 parts of other inorganic inert materials and 5-10 parts of anti-blooming auxiliary agent in percentage by weight; the anti-frosting auxiliary agent is prepared from amino-terminated hyperbranched polyamide and unsaturated glycidyl ester through an epoxy ring-opening reaction.

Further, the anti-blooming auxiliary agent is prepared through the following steps:

adding the amino-terminated hyperbranched polyamide and the unsaturated glycidyl ester into toluene, performing ultrasonic dispersion, heating to 80 ℃ for reflux reaction, and removing the solvent after the reaction is finished to obtain the anti-blooming auxiliary agent.

Further, the usage ratio of the amino-terminated hyperbranched polyamide and the unsaturated glycidyl ester is 50g:0.01-0.02 mol; the molecular weight of the amino-terminated hyperbranched polyamide is 800-5600. The raw material proportion of the amino-terminated hyperbranched polyamide and the unsaturated glycidyl ester can be adjusted to prepare different types of anti-blooming auxiliary agents, the dispersing effect of the anti-blooming auxiliary agents in the material is improved, the addition amount of the unsaturated glycidyl ester is not excessive, the subsequent vulcanization crosslinking density is excessive due to the excessive addition amount, the ductility of the rubber material is poor, and the dosage proportion is 50g: within the range of 0.01-0.02 mol, the cost can be reduced, the follow-up processing process is convenient,

Further, the amino-terminated hyperbranched polyamide is one of amino-terminated hyperbranched polyamide Hyper N101, amino-terminated hyperbranched polyamide Hyper N102 and amino-terminated hyperbranched polyamide Hyper N103.

Further, the unsaturated glycidyl ester is one of glycidyl methacrylate and allyl glycidyl ether.

Further, the other inorganic inert material is at least one of nano silicon dioxide, nano zinc oxide and nano titanium dioxide. Other inorganic inert materials are adjusted according to the application scene.

Further, the other inorganic inert materials are modified by a vinyl silane coupling agent. The modified rubber material can improve the dispersion property so as to prepare the rubber material with higher requirements.

Further, the steps of modifying the vinyl silane coupling agent are as follows:

Adding other inorganic inert materials into toluene, adding a vinyl silane coupling agent after ultrasonic dispersion, wherein the addition amount of the vinyl silane coupling agent is 4% of the mass of the other inorganic inert materials, heating and refluxing for 2h, and washing and drying after the reaction is finished.

A preparation method of a processing aid for anti-blooming rubber comprises the following steps:

and (3) mixing calcium carbonate, other inorganic inert materials, an anti-blooming auxiliary agent and the copolymer, adding di-tert-butyl isopropyl peroxide, uniformly mixing, extruding, cooling and granulating to obtain the processing auxiliary agent for the anti-blooming rubber. In the processing process, friction occurs in the blending of raw materials, the reaction temperature is too high, the added anti-blooming auxiliary agent is favorable for reducing the mixing time, the materials are better mixed in the limited dispersing time, and the di-tert-butyl isopropyl peroxide is added for mixing after mixing, so that the advanced crosslinking is avoided, and the stability of the product is improved.

Further, the copolymer is selected from ethylene-vinyl acetate copolymers; copolymers of ethylene with acrylic esters; one of a styrene ethylene butylene hydrogenated copolymer and a styrene ethylene propylene hydrogenated copolymer.

The invention has the beneficial effects that:

The invention prepares the processing aid for the anti-frosting rubber, and solves the problem that frosting is easy to occur when BIPB is added into a rubber material. The processing auxiliary agent comprises a self-made anti-frosting auxiliary agent, is obtained by epoxy ring-opening reaction of amino-terminated hyperbranched polyamide and unsaturated glycidyl ester, has good dispersion performance and adsorption performance, and can inhibit the problem that rubber materials are easy to frost.

The structure of the anti-frosting auxiliary agent disclosed by the invention maintains a branched structure in an amino-terminated hyperbranched polyamide structure, reduces the viscosity of a system, improves the dispersion effect, and has good adsorption performance on a cavity formed by the branched structure, has stronger adsorption acting force on decomposed small molecular substances, and can inhibit migration of the decomposed dihydroxy-1, 4-diisopropylbenzene in a rubber material. The anti-blooming auxiliary agent further improves the molecular weight through the reaction with the unsaturated glycidyl ester, simultaneously introduces a double bond structure, provides a reaction site with the rubber through co-vulcanization, further improves the migration resistance of the anti-blooming auxiliary agent, prevents the anti-blooming auxiliary agent from forming a continuous migration layer, and not only can eliminate aggregation phenomenon, but also improves the anti-blooming performance.

In order to further improve the performance of the processing aid for the anti-blooming rubber, the dispersibility of other inert materials can be improved by treating the added other inert materials, the dispersing effect of the other inert materials in the processing aid for the anti-blooming rubber is improved, and the overall performance of the rubber after cross-linking can be improved.

Detailed Description

The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Example 1

A processing aid for anti-blooming rubber:

Adding amino-terminated hyperbranched polyamide Hyper N101 (molecular weight 800-1000) and glycidyl methacrylate into toluene, performing ultrasonic dispersion, heating to 80 ℃ for reflux reaction, and removing a solvent after the reaction is finished to obtain a frost prevention auxiliary agent; wherein the dosage ratio of the amino-terminated hyperbranched polyamide to the glycidyl methacrylate is 50g:0.01 mol.

According to the weight portions, 40 to 45 portions of calcium carbonate, 5 to 15 portions of nano silicon dioxide, 5 to 10 portions of prepared anti-frosting auxiliary agent and 50 portions of ethylene-vinyl acetate copolymer (E l vax 360A) are blended, then 40 to 50 portions of di-tert-butyl isopropyl benzene peroxide are added to be evenly mixed, and then the mixture is extruded and prepared by using a barrel temperature of 75 ℃ and a screw speed of 100 rpm. After extrusion, the resulting tape was cooled and chopped into pellets to yield a processing aid for anti-blooming rubber.

Example 2-example 5

This example is different from example 1 in that the ratio of the raw materials is adjusted, and the remaining raw materials and the preparation process remain the same as in example 1.

TABLE 1

Example 6

The difference between this example and example 1 is that the anti-blooming auxiliary is different, in particular:

The amino-terminated hyperbranched polyamide Hyper N101 (molecular weight 800-1000) was replaced with the amino-terminated hyperbranched polyamide Hyper N102 (molecular weight 1900-2200), and the remaining raw materials and the preparation process were kept the same as in example 1.

Example 7

The amino-terminated hyperbranched polyamide Hyper N101 (molecular weight 800-1000) is replaced by amino-terminated hyperbranched polyamide Hyper N103 (molecular weight 5200-5600), and the dosage ratio of the amino-terminated hyperbranched polyamide to the glycidyl methacrylate is 50g:0.02 mol, the rest of the raw materials and the preparation process remain the same as in example 1.

Example 8

This example differs from example 1 in that other inorganic inert materials are different, in particular:

the nano silicon dioxide is modified by a vinyl silane coupling agent, and the modification steps are as follows:

Adding nano silicon dioxide into toluene, adding a vinyl silane coupling agent (KH-570) after ultrasonic dispersion, wherein the addition amount of the vinyl silane coupling agent is 4% of the mass of the nano silicon dioxide, heating and refluxing for 2h, and washing and drying after the reaction is finished. The remaining raw materials and preparation process remain the same as in example 1.

Comparative example 1

In this comparative example, the anti-blooming aid was replaced with stearic acid, and the remaining raw materials and the preparation process were kept unchanged, as compared with example 1.

The results of recording the mixing time (mixing time for visual total dispersion) of the materials in example 1-example 8 and comparative example 1 are shown in table 2 below:

TABLE 2

Project	Mixing time
		Example 1	Less than 2min
Example 2	Less than 2min
		Example 2	Less than 2min
Example 3	Less than 2min
		Example 4	Less than 2min
Example 5	Less than 2min
		Example 6	Less than 2min
Example 7	Less than 2min
		Example 8	Less than 2min
Comparative example 1	More than 5min

The anti-blooming auxiliary agent prepared by the invention

Testing the auxiliary agent samples prepared in the examples 1-8 and the comparative example 1 to prepare samples to be tested; the formulation of the test specimen was 100 parts of EPDM, 140 parts of carbon black (70 parts of N-550 and 70 parts of N-772), 50 parts of paraffin oil (SUNPAR 2280) and 9 parts of the processing aid for anti-blooming rubber prepared in examples 1 to 8.

The test mechanical properties are according to the standard GB/T528-2009; and (3) frosting test: and starting a switch of the constant temperature and humidity box, wherein the set temperature is 70 ℃ and the humidity is 95%. And after the temperature and the humidity reach set values, placing the sample into a constant temperature and humidity box. The bloom test was started for 168 hours (i.e., 7 days). After the test time, the sample was taken out and the change in the surface of the sample was observed. Each set of samples was tested in triplicate. The results are shown in Table 3 below:

TABLE 3 Table 3

From the test results, the processing aid for the anti-blooming rubber, which is prepared by the invention, has a good effect of avoiding blooming. Stearic acid added in comparative example 1 is also commonly used as an additive for reducing rubber bloom, but the improvement effect is limited, and the proper increase of the amount of stearic acid can dissolve or improve the solubility of inorganic matters in rubber, thereby indirectly preventing blushing. However, the addition amount is too much, the anti-frosting auxiliary agent is easy to spray out, so that the anti-frosting auxiliary agent has stronger migration resistance, the addition amount range is larger (namely, the use amount is easier to control), and the mechanical property index is improved under the same proportioning condition, so that the effects of saving materials and reducing cost can be achieved.

It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims

1. A processing aid for anti-blooming rubber, characterized in that, in terms of weight percentage, it comprises 40-50 parts of di-tert-butyl peroxide isopropylbenzene, 40-45 parts of calcium carbonate, 5-15 parts of other inorganic inert materials, and 5-10 parts of anti-blooming aid; the anti-blooming aid is obtained by epoxy ring-opening reaction of amino-terminated hyperbranched polyamide and unsaturated glycidyl ester.

2. The anti-blooming rubber processing aid according to claim 1, characterized in that the anti-blooming aid is prepared by the following steps:

The amino-terminated hyperbranched polyamide and unsaturated glycidyl ester are added into a solvent, ultrasonically dispersed, heated under reflux for reaction, and after the reaction is completed, the solvent is removed to obtain an anti-blooming adjuvant.

3. A processing aid for anti-blooming rubber according to claim 1, characterized in that the amount ratio of the amino-terminated hyperbranched polyamide and the unsaturated glycidyl ester is 50g:0.01-0.02mol; and the molecular weight of the amino-terminated hyperbranched polyamide is 800-5600.

4. A processing aid for anti-blooming rubber according to claim 1, characterized in that the amino-terminated hyperbranched polyamide is one of amino-terminated hyperbranched polyamide Hyper N101, amino-terminated hyperbranched polyamide Hyper N102 and amino-terminated hyperbranched polyamide Hyper N103.

5. A processing aid for anti-blooming rubber according to claim 1, characterized in that the unsaturated glycidyl ester is one of glycidyl methacrylate and allyl glycidyl ether.

6 . The processing aid for anti-blooming rubber according to claim 1 , characterized in that the other inorganic inert material is at least one of nano silicon dioxide, nano zinc oxide and nano titanium dioxide.

7. A processing aid for anti-blooming rubber according to claim 1, characterized in that the other inorganic inert materials are modified with a vinyl silane coupling agent.

8. A processing aid for anti-blooming rubber according to claim 7, characterized in that the steps of modifying the vinyl silane coupling agent are as follows: adding other inorganic inert materials to toluene, adding the vinyl silane coupling agent after ultrasonic dispersion, the amount of vinyl silane coupling agent added is 4% of the mass of other inorganic inert materials, heating and reflux reaction, and after the reaction is completed, washing and drying.

9. A method for preparing the anti-blooming rubber processing aid according to any one of claims 1 to 8, characterized in that it comprises the following steps:

Calcium carbonate, other inorganic inert materials, anti-blooming aids and copolymers are blended, and then di-tert-butyl peroxide isopropylbenzene is added and mixed evenly, extruded, cooled and pelletized to obtain an anti-blooming rubber processing aid.

10. The method for preparing a processing aid for anti-blooming rubber according to claim 9, characterized in that the copolymer is selected from one of ethylene-vinyl acetate copolymer; copolymer of ethylene and acrylate; styrene ethylene butene hydrogenated copolymer and styrene ethylene propylene hydrogenated copolymer.