Preparation method and application of basalt fiber reinforced thermoplastic polyolefin elastomer

Abstract

The invention discloses a preparation method and application of a basalt fiber reinforced thermoplastic polyolefin elastomer, and belongs to the technical field of polyolefin elastomer materials. The preparation method comprises the following steps: (1) carrying out melt blending on polyethylene resin or polypropylene resin and EVA (Ethylene Vinyl Acetate) or ethylene propylene rubber to prepare a thermoplastic polyolefin elastomer; (2) the basalt fibers are placed in a mixed aqueous solution of phosphoric acid, hydrogen peroxide and phenol, and the surfaces of the basalt fibers are subjected to roughening treatment; and (3) adding an initiator and an active agent into the thermoplastic polyolefin elastomer by adopting a parallel twin-screw extruder, carrying out melt processing, then adding basalt fibers at a fiber feeding port, and carrying out melt blending by adopting the twin-screw extruder to obtain the modified thermoplastic polyolefin elastomer. The prepared modified thermoplastic polyolefin elastomer has good mechanical properties, and when the modified thermoplastic polyolefin elastomer is applied to production of winding pipes, the prepared winding pipes have good ring stiffness and ring flexibility.

Description

Technical Field

[0001] The invention relates to the technical field of polyolefin elastomer materials, and in particular to a preparation method and application of a basalt fiber reinforced thermoplastic polyolefin elastomer. Background Art

[0002] Polyolefin thermoplastic elastomer is a rubber-like elastomer with good softness, good transparency, surface gloss, chemical stability, aging resistance and ozone resistance. It can still have good windability at -50°C. At the same time, the elastomer has good miscibility with fillers, and has good coloring and molding processability. It is a safe, environmentally friendly, widely used and healthy environmentally friendly material. Its most notable feature is that it has high flexibility and good aging resistance, as well as good mechanical strength. It is widely used in the automotive industry, machinery manufacturing industry, and waterproof materials. Basalt fiber is a new type of natural mineral fiber developed in recent years. Compared with glass fiber, it has more natural and high-performance characteristics. It has a wide range of applications and good prospects in the field of polymer material modification and reinforcement.

[0003] By using basalt fiber to modify and strengthen polyolefin thermoplastic elastomer, while maintaining its high toughness, its rigidity can be greatly improved, and it can be used to make winding pipes, so that the winding pipes have good rigidity and toughness at the same time, and its performance is improved. However, basalt fiber is an inorganic material, and polyolefin elastomer is a non-polar organic polymer material. The two have poor solubility, so it is very important to solve the interface compatibility problem.

[0004] In view of the above problems, the present invention provides a preparation method and application of a basalt fiber reinforced thermoplastic polyolefin elastomer. Summary of the invention

[0005] The purpose of the present invention is to provide a preparation method and application of basalt fiber reinforced thermoplastic polyolefin elastomer. The prepared modified thermoplastic polyolefin elastomer has good mechanical properties. It is applied to the production of winding pipes to solve the problems raised by the above-mentioned background technology, so that the prepared winding pipe has good rigidity and toughness at the same time, thereby improving its performance.

[0006] To achieve the above object, the present invention provides a method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer, comprising the following steps:

[0007] (1) preparing a thermoplastic polyolefin elastomer;

[0008] (2) Surface treatment of basalt fiber;

[0009] (3) Modification of thermoplastic polyolefin elastomer with basalt fiber.

[0010] Preferably, in step (1), the thermoplastic polyolefin elastomer is prepared by melt blending a polyolefin resin and EVA or ethylene-propylene rubber.

[0011] Preferably, by mass percentage, the polyolefin resin accounts for 60%-90%, and the EVA or ethylene-propylene rubber accounts for 10%-40%; wherein the polyolefin resin is one of polyethylene resin or polypropylene resin.

[0012] Preferably, in step (2), the basalt fiber is placed in a mixed aqueous solution of phosphoric acid, hydrogen peroxide and phenol to roughen its surface, immersed at 80° C. for half an hour, and finally washed with water.

[0013] Preferably, in the mixed aqueous solution, the weight concentration of phosphoric acid is 15-30%, the weight concentration of hydrogen peroxide is 2-4%, and the weight concentration of phenol is 2-8%.

[0014] Preferably, in step (3), a parallel twin-screw extruder is used to add an initiator and an activator to the thermoplastic polyolefin elastomer at 180-220° C. for melt processing, and then basalt fiber is added to the fiber feeding port and melt blended using a twin-screw extruder.

[0015] Preferably, the initiator is one or more of dicumyl peroxide or long-chain alkyl ammonium persulfate; the activator is one or more of vinyl pyrrolidone, vinyl triethoxysilane, vinyl trimethoxysilane or glycidyl acrylate.

[0016] Preferably, the amount of the initiator is 0.01%-0.2% of the thermoplastic polyolefin elastomer; the amount of the active agent is 1%-3% of the thermoplastic polyolefin elastomer; and the amount of the basalt fiber is 20%-30% of the thermoplastic polyolefin elastomer.

[0017] The present invention also provides a basalt fiber reinforced thermoplastic polyolefin elastomer prepared by the preparation method.

[0018] The invention also provides application of the modified thermoplastic polyolefin elastomer prepared above in the production of winding pipes.

[0019] Therefore, the present invention provides a preparation method and application of a basalt fiber reinforced thermoplastic polyolefin elastomer. The prepared modified thermoplastic polyolefin elastomer has good mechanical strength and is used to produce a winding pipe, which also has good rigidity and toughness.

[0020] The technical solution of the present invention is further described in detail below through embodiments. DETAILED DESCRIPTION

[0021] The present invention is further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. Any other changes, modifications, substitutions, combinations, simplifications made without violating the spirit and principle of the present invention should all be equivalent replacement methods and are included in the protection scope of the present invention. In addition, it should be understood that after reading the content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application, and all belong to the scope of protection of the present invention.

[0022] Reference to "embodiment" herein means that the specific features, structures or characteristics described in conjunction with the embodiment may be included in at least one embodiment of the present application. The term "embodiment" appearing in various places in the specification does not necessarily refer to the same embodiment, nor does it particularly limit its independence or association with other embodiments. In principle, in the present application, as long as there is no technical contradiction or conflict, the various technical features mentioned in the embodiments can be combined in any way to form a corresponding implementable technical solution.

[0023] Unless otherwise defined, the technical terms used in this document have the same meanings as those generally understood by those skilled in the art to which this application belongs; the use of relevant terms in this document is only for describing specific embodiments and is not intended to limit this application.

[0024] Unless otherwise specified in the present invention, the reagents, instruments, and equipment used are those commonly used by technicians in this field.

[0025] Example 1

[0026] This embodiment provides a method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer, which specifically comprises the following steps:

[0027] (1) Preparation of thermoplastic polyolefin elastomer

[0028] Thermoplastic polyolefin elastomer is prepared by melt blending 80% polyethylene resin and 20% EVA;

[0029] (2) Surface treatment of basalt fiber

[0030] The basalt fiber is placed in a mixed aqueous solution of phosphoric acid, hydrogen peroxide and phenol to roughen its surface, immersed at 80°C for half an hour, and finally washed with water; wherein the weight concentration of phosphoric acid is 20%, the weight concentration of hydrogen peroxide is 3%, and the weight concentration of phenol is 4%.

[0031] (3) Modification of thermoplastic polyolefin elastomers with basalt fibers

[0032] A parallel twin-screw extruder is used to add dicumyl peroxide and glycidyl acrylate to a thermoplastic polyolefin elastomer at 200° C. for melt processing, and then basalt fiber is added to the fiber feeding port, wherein the weight of dicumyl peroxide is 1% of the weight of the thermoplastic polyolefin elastomer, the weight of glycidyl acrylate is 3% of the weight of the thermoplastic polyolefin elastomer, and the weight of the surface-treated basalt fiber is 25% of the weight of the thermoplastic polyolefin elastomer, and the twin-screw extruder is used for melt blending.

[0033] The physical and mechanical properties of the prepared modified thermoplastic polyolefin elastomer were tested, and the test results are as follows:

[0034] The tensile strength of the modified thermoplastic polyolefin elastomer reinforced material reaches 30MPa and the impact strength reaches 20KJ / m 2 The fiber content in the reinforcing material is 25% and the fiber length is 2-3mm.

[0035] Example 2

[0036] The present embodiment provides a method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer. The preparation method is the same as that of Example 1. The only difference from Example 1 is that in the present embodiment, dodecyl ammonium persulfate is used as an initiator, and the added amount is 0.2% by weight of the thermoplastic polyolefin elastomer, and vinyl triethoxysilane is used as an activator, and the added amount is 2% by weight of the thermoplastic polyolefin elastomer. The rest is the same as that of Example 1 and will not be repeated here.

[0037] The physical and mechanical properties of the prepared modified thermoplastic polyolefin elastomer were tested, and the test results are as follows:

[0038] The tensile strength of the modified thermoplastic polyolefin elastomer reinforced material can reach 32MPa and the impact strength is 18KJ / m 2 , the fiber length is between 2-3mm.

[0039] Example 3

[0040] This embodiment provides a method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer, which specifically comprises the following steps:

[0041] (1) Preparation of thermoplastic polyolefin elastomer

[0042] Thermoplastic polyolefin elastomer is prepared by melt blending 75% polyethylene resin and 25% ethylene propylene rubber (EPM);

[0043] (2) Surface treatment of basalt fiber

[0044] The basalt fiber is placed in a mixed aqueous solution of phosphoric acid, hydrogen peroxide and phenol to roughen its surface, immersed at 80°C for half an hour, and finally washed with water; wherein the weight concentration of phosphoric acid is 20%, the weight concentration of hydrogen peroxide is 3%, and the weight concentration of phenol is 4%.

[0045] (3) Modification of thermoplastic polyolefin elastomers with basalt fibers

[0046] A parallel twin-screw extruder is used to add dicumyl peroxide and vinyl pyrrolidone to a thermoplastic polyolefin elastomer at 200° C. for melt processing, and then basalt fiber is added to the fiber feeding port, wherein the weight of dicumyl peroxide is 0.1% of the weight of the thermoplastic polyolefin elastomer, the weight of vinyl pyrrolidone is 3% of the weight of the thermoplastic polyolefin elastomer, and the surface-treated basalt fiber accounts for 20% of the weight of the thermoplastic polyolefin elastomer. The twin-screw extruder is used for melt blending.

[0047] The physical and mechanical properties of the prepared modified thermoplastic polyolefin elastomer were tested, and the test results are as follows:

[0048] The tensile strength of the modified thermoplastic polyolefin elastomer reinforced material is 25MPa and the impact strength is 16KJ / m 2 .

[0049] Example 4

[0050] The present embodiment provides a method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer. The preparation method is the same as that of Example 1. The only difference from Example 1 is that in the present embodiment, dodecyl ammonium persulfate is used as an initiator, and the added amount is 0.2% of the weight of the thermoplastic polyolefin elastomer, and vinyl trimethoxy is used as an activator, and the added amount is 2% of the weight of the thermoplastic polyolefin elastomer. The surface-treated basalt fiber accounts for 30% of the weight of the thermoplastic polyolefin elastomer. The rest is the same as that of Example 1 and will not be repeated here.

[0051] The physical and mechanical properties of the prepared modified thermoplastic polyolefin elastomer were tested, and the test results are as follows:

[0052] The tensile strength of the modified thermoplastic polyolefin elastomer reinforced material is 35MPa and the impact strength is 15KJ / m 2 .

[0053] Example 5

[0054] The present embodiment provides a preparation method of a basalt fiber reinforced thermoplastic polyolefin elastomer. The preparation method is the same as that of Example 1. The only difference from Example 1 is that the present embodiment uses 70% polyethylene resin and 30% EVA to melt blend to prepare the thermoplastic polyolefin elastomer; dodecyl ammonium persulfate and diisopropylbenzene peroxide are used as initiators, and the added amount is 0.05% of the weight of the thermoplastic polyolefin elastomer; vinyl pyrrolidone and glycidyl acrylate are used as activators, and the added amount is 1% of the weight of the thermoplastic polyolefin elastomer; the surface-treated basalt fiber accounts for 30% of the weight of the thermoplastic polyolefin elastomer, and the rest is the same as Example 1, which will not be repeated here.

[0055] The physical and mechanical properties of the prepared modified thermoplastic polyolefin elastomer were tested, and the test results are as follows:

[0056] The modified thermoplastic polyolefin elastomer material has a tensile strength of 31MPa and an impact strength of 18KJ / m 2 .

[0057] Comparative Example 1

[0058] This comparative example provides a method for preparing a thermoplastic polyolefin elastomer, and the specific steps are: melt-blending 80% of polyethylene resin and 20% of EVA to prepare the thermoplastic polyolefin elastomer.

[0059] The physical and mechanical properties of the prepared thermoplastic polyolefin elastomer were tested, and the test results are as follows:

[0060] The tensile strength of the thermoplastic elastomer is 20MPa and the notched cantilever beam impact strength is 18KJ / m 2 .

[0061] Comparative Example 2

[0062] This comparative example provides a method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer, which specifically comprises the following steps:

[0063] (1) Preparation of thermoplastic polyolefin elastomer

[0064] Thermoplastic polyolefin elastomer is prepared by melt blending 80% polyethylene resin and 20% EVA;

[0065] (3) Modification of thermoplastic polyolefin elastomers with basalt fibers

[0066] A parallel twin-screw extruder is used to add thermoplastic polyolefin elastomer at 200° C., and then basalt fiber is added at the fiber feeding port, wherein the weight of the basalt fiber is 25% of the weight of the thermoplastic polyolefin elastomer, and the twin-screw extruder is used for melt blending.

[0067] The physical and mechanical properties of the modified thermoplastic polyolefin elastomer modified by basalt fiber were tested, and the test results are as follows:

[0068] Without surface modification of basalt fiber and without adding initiator and activator, the tensile strength of the modified thermoplastic polyolefin elastomer material is 21MPa and the impact strength is 5KJ / m 2 .

[0069] The municipal winding pipe prepared by using the basalt fiber reinforced thermoplastic elastomer prepared in Example 3 has a higher rigidity than non-basalt reinforced materials, and the wall thickness and weight per meter can be significantly reduced under the condition of reaching the ring stiffness of 8KN required for use. The weight per meter of ordinary polyethylene and non-reinforced elastomer is 8.5 kg, while the weight per meter of the elastomer prepared by using the reinforced elastomer prepared in Example 3 is only 7.5 kg when the ring stiffness and ring flexibility meet the use requirements.

[0070] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer, characterized in that: The following steps are involved: (1) preparing a thermoplastic polyolefin elastomer; (2) Surface treatment of basalt fiber; (3) Modification of thermoplastic polyolefin elastomer with basalt fiber.

2. The method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer according to claim 1, characterized in that: In step (1), the thermoplastic polyolefin elastomer is prepared by melt blending a polyolefin resin and EVA or ethylene-propylene rubber.

3. The method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer according to claim 2, characterized in that: In terms of mass percentage, polyolefin resin accounts for 60%-90%, and EVA or ethylene-propylene rubber accounts for 10%-40%; wherein the polyolefin resin is one of polyethylene resin or polypropylene resin.

4. The method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer according to claim 1, characterized in that: In step (2), the basalt fiber is placed in a mixed aqueous solution of phosphoric acid, hydrogen peroxide and phenol to roughen its surface, immersed at 80° C. for half an hour, and finally washed with water.

5. The method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer according to claim 4, characterized in that: In the mixed aqueous solution, the weight concentration of phosphoric acid is 15-30%, the weight concentration of hydrogen peroxide is 2-4%, and the weight concentration of phenol is 2-8%.

6. The method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer according to claim 1, characterized in that: In step (3), a parallel twin-screw extruder is used to add an initiator and an activator to a thermoplastic polyolefin elastomer at 180-220° C. for melt processing, and then basalt fiber is added to the fiber feed port and melt blended using a twin-screw extruder.

7. The method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer according to claim 6, characterized in that: The initiator is one or more of dicumyl peroxide or long-chain alkyl ammonium persulfate; the activator is one or more of vinyl pyrrolidone, vinyl triethoxysilane, vinyl trimethoxysilane or glycidyl acrylate.

8. The method for preparing a basalt fiber reinforced thermoplastic polyolefin elastomer according to claim 6, characterized in that: The dosage of the initiator is 0.01%-0.2% of the thermoplastic polyolefin elastomer; the dosage of the active agent is 1-3% of the thermoplastic polyolefin elastomer; and the dosage of the basalt fiber is 20-30% of the thermoplastic polyolefin elastomer.

9. A basalt fiber reinforced thermoplastic polyolefin elastomer, characterized in that: The modified thermoplastic polyolefin elastomer is prepared by the preparation method according to any one of claims 1 to 8.

10. The basalt fiber reinforced thermoplastic polyolefin elastomer according to claim 9, characterized in that: The modified thermoplastic polyolefin elastomer is applied to the production of winding pipes.