Basalt modified polyester fiber and preparation method thereof

Abstract

The application relates to the technical field of fibers, and discloses basalt-added modified polyester fiber and a preparation method thereof. The polyester fiber is prepared from PET chips, modified basalt fiber additive, an antioxidant and vinyl bis-stearamide as raw materials through mixing, extrusion to form a master batch, and then through a melt spinning process, wherein the modified basalt fiber additive is prepared by modifying a polymer modifier on the surface of basalt fiber. In the melt extrusion process, the molecular chains of the polymer modifier are interpenetrated and interwoven with the molecular chains of PET, forming a physical crosslinking network, so that the basalt fiber can efficiently play an advantage, and the mechanical strength of the polyester fiber is improved. A large amount of phosphorus elements and silicon elements are contained in the structure of the polymer modifier, so that the flame-retardant performance of the fiber can be effectively improved.

Description

Technical Field

[0001] This invention relates to the field of fiber technology, specifically to a basalt-modified polyester fiber and its preparation method. Background Technology

[0002] Polyester (PET), as a core material in the field of synthetic fibers, has become the world's largest-produced synthetic fiber since its industrial production, thanks to its excellent physical and chemical properties and cost advantages. Its core characteristics include good abrasion resistance, high chemical stability, and excellent processing performance. However, with the continuous application of polyester fibers, their limitations have become increasingly prominent. In particular, the negative impact of frequent fires in recent years has made the poor flame retardant properties of polyester fibers a key factor affecting its further expansion of applications. Moreover, the mechanical strength of polyester fibers is gradually failing to meet the needs of some industries. Therefore, modifying polyester fibers is of great significance.

[0003] Basalt fiber, as a novel inorganic environmentally friendly fiber, exhibits significantly superior performance parameters compared to polyester. Therefore, it can be used as an additive to modify polyester fibers. However, polyester fibers are highly rigid and prone to agglomeration during melt spinning, leading to stress concentration and potentially causing negative effects rather than the intended reinforcement. Furthermore, improving the flame-retardant properties of polyester fibers by adding flame retardants is common; however, existing flame retardants present significant problems in practical applications. Adding a single flame retardant often results in poor flame-retardant performance and requires a large dosage. Therefore, this invention provides a polyester fiber that addresses the problems existing in the prior art. Summary of the Invention

[0004] In order to solve the problems mentioned in the background art, the purpose of this invention is to provide a basalt-modified polyester fiber and its preparation method.

[0005] The objective of this invention can be achieved through the following technical solutions: A basalt-modified polyester fiber comprising the following raw materials in parts by weight: 75-95 parts PET chips, 3-6.5 parts modified basalt fiber additive, 0.5-1 part antioxidant, and 1-2 parts vinyl bis-stearamide; The modified basalt fiber additive is basalt fiber with a surface modified by a polymer modifier.

[0006] As a further aspect of the present invention, the modified basalt fiber additive is prepared by the following method: Step 1: Use silane-based surface modifiers to modify the surface of basalt fibers to obtain organic functionalized basalt fibers; Step 2: In a dimethyl sulfoxide medium, using the organic functional groups of the organically functionalized basalt fiber as active initiation sites, functional monomers and chain extenders are polymerized in situ on the surface of the basalt fiber under the action of a catalyst to obtain modified basalt fiber additives.

[0007] As a further aspect of the present invention, in step one, the silane-based surface modifier is 3-glycidyl etheroxypropyltrimethoxysilane or 3-glycidyl etheroxypropyltriethoxysilane.

[0008] As a further aspect of the present invention, in step two, the catalyst is a boron trifluoride diethyl ether complex.

[0009] As a further embodiment of the present invention, in step two, the functional monomer is prepared by reacting 5-norbornene-2,2-diethanol and 5,5-dimethyl-1,3,2-dioxophosphanecyclohexane-2-one as raw materials under the action of an accelerator.

[0010] As a further embodiment of the present invention, the molar ratio of 5-norbornene-2,2-diethanol and 5,5-dimethyl-1,3,2-dioxophosphanecyclohexane-2-one is 1:1.

[0011] As a further aspect of the present invention, the accelerator is azobisisobutyronitrile.

[0012] As a further embodiment of the present invention, the chain-extended monomer is 1,1,3,3-tetramethyl-1,3-bis-[2-[7-oxybicyclo[4.1.0]hept-3-yl]ethyl]disiloxane.

[0013] It should be noted that in the above technical solution, basalt fibers are first modified with silane-based surface modifiers to carry epoxy substituents on the surface of the basalt fibers. Then, under the action of a catalyst, the epoxy substituents on the surface of the basalt fibers serve as active initiation sites to carry out continuous ring-opening addition reactions with the active hydroxyl groups in the functional monomer structure and the epoxy groups in the chain-extended monomer structure. This results in the modification of the basalt fiber surface with polymeric modifiers linked by ether bonds, thus obtaining modified basalt fiber additives.

[0014] The chain-extending monomers are prepared by adding PH to the unsaturated alkenyl substituents in the structures of 5-norbornene-2,2-diethanol and 5,5-dimethyl-1,3,2-dioxophosphanecyclohexane-2-one under the action of an accelerator.

[0015] As a further aspect of the present invention, the antioxidant is any one of antioxidant 168, antioxidant 1076, antioxidant 626, or antioxidant 1010.

[0016] A method for preparing basalt-modified polyester fibers includes the following steps: The first step is to add the raw materials measured by weight into a high-speed mixer, control the speed to 200-300 r / min, and mechanically mix for 1-2 hours. Then, transfer the mixture to a twin-screw extruder and melt extrusion to form masterbatch. Next, melt spinning is used to spin the masterbatch to obtain nascent fibers. Step 2: The nascent fibers are drawn and spun, followed by winding, forming, bundle drawing and heat setting.

[0017] The beneficial effects of this invention are: This invention prepares a modified basalt fiber additive by modifying the surface of basalt fiber with a polymeric modifier. Firstly, the polymeric modifier, acting as an organic transition layer, effectively improves the dispersibility of basalt fiber in polyester. During melt extrusion, the polymeric modifier's molecular chains interweave with the PET molecular chains, forming a physical cross-linking network. The basalt fiber acts as the core point of this cross-linking network, providing support and reinforcement, thus efficiently utilizing the advantages of basalt fiber and enhancing the mechanical strength of the polyester fiber. Secondly, the polymeric modifier contains a large amount of phosphorus and silicon. Phosphorus acts as an acid source, rapidly catalyzing the formation of a carbon layer, while silicon deposits on the carbon layer surface in the form of oxides, improving the stability of the carbon layer and working synergistically with it to isolate heat and oxygen, preventing the continuation of combustion and effectively improving the flame retardant properties of the fiber. Furthermore, because the polymeric modifier is modified onto the surface of the basalt fiber, it cannot be easily removed, ensuring that it will not detach during repeated washing, thereby guaranteeing the long-lasting flame retardant properties of the polyester fiber.

[0018] Of course, any product implementing this invention does not necessarily need to achieve all of the advantages described above at the same time. Attached Figure Description

[0019] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 Infrared analysis test chart of functional unit. Detailed Implementation

[0021] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] Preparation Example Preparation of modified basalt fiber additive: Step 1: Disperse 1.5g of basalt fiber in a 50% (v / v) ethanol aqueous solution, and add 0.3g of 3-glycidyl etheroxypropyltrimethoxysilane to the resulting uniform dispersion. After the addition is complete, adjust the pH to 4, then control the temperature at 70℃, keep it warm and stir for 6 hours, cool down and discharge the material, collect the solid, wash and vacuum dry it to obtain organic functionalized basalt fiber. Step 2: Add 1.2g of organic functionalized basalt fiber to dimethyl sulfoxide medium and sonicate at 100kHz for 30min. Then add 0.4g of functional monomer and 0.03g of boron trifluoride diethyl ether complex. After addition, raise the temperature to 75℃ and stir for 2h. Then add 0.5g of 1,1,3,3-tetramethyl-1,3-bis-[2-[7-oxybicyclo[4.1.0]hept-3-yl]ethyl]disiloxane. Adjust the temperature to 85℃ and stir continuously for 12h. Then stop heating, cool down and discharge the material. After washing and vacuum drying, the modified basalt fiber additive is obtained.

[0023] The functional monomers were prepared using the following methods: 0.6 g of 5-norbornene-2,2-diethanol, 0.58 g of 5,5-dimethyl-1,3,2-dioxophosphazenecyclohexane-2-one and tetrahydrofuran were added to a nitrogen-filled reactor. Stirring was started, and after mixing was uniform, 0.1 g of azobisisobutyronitrile was added. After the addition was complete, the temperature was raised to 65°C, and stirring was maintained for 8 hours. Heating was then stopped, and the mixture was allowed to cool. The product was filtered out, washed, and vacuum dried to obtain the functional monomer.

[0024] Figure 1 The infrared analysis test pattern of the functional unit, where 3493 cm⁻¹ -1 The characteristic absorption peak appearing at 1290 cm⁻¹ is the characteristic absorption peak of the hydroxyl group (OH). -1 The characteristic absorption peak appearing at 1048 cm⁻¹ is the characteristic absorption peak of P=O. -1 The characteristic absorption peak appearing at this point is the characteristic absorption peak of POC. Figure 1The absence of a C=C characteristic absorption peak and a pH characteristic absorption peak confirms that the unsaturated alkenyl substituent in the 5-norbornene-2,2-diethanol structure undergoes an addition reaction with the pH in the 5,5-dimethyl-1,3,2-dioxophosphanecyclohexane-2-one structure.

[0025] Example 1 A basalt-modified polyester fiber comprising the following raw materials in parts by weight: 75 parts PET chips, 3 parts modified basalt fiber additive, 0.5 parts antioxidant 168, and 1 part vinyl bis-stearamide; The method for preparing the polyester fiber includes the following steps: The first step is to add the raw materials measured according to the weight percentage into a high-speed mixer, control the speed at 200 r / min, and mechanically mix for 2 hours. Then, transfer the mixture to a twin-screw extruder and form masterbatch through melt extrusion. Next, the masterbatch is spun into nascent fibers using melt spinning. Step 2: The nascent fibers are drawn and spun, followed by winding, forming, bundle drawing and heat setting.

[0026] The preparation method of the modified basalt fiber additive is shown in the preparation example, and the same applies to the following.

[0027] Example 2 A basalt-modified polyester fiber comprising the following raw materials in parts by weight: 80 parts PET chips, 6 parts modified basalt fiber additive, 0.8 parts antioxidant 1076, and 1.5 parts vinyl bis-stearamide; The method for preparing the polyester fiber includes the following steps: The first step is to add the raw materials measured by weight into a high-speed mixer, control the speed at 300 r / min, and mechanically mix for 1.5 hours. Then, transfer the mixture to a twin-screw extruder and melt extrusion to form masterbatch. Next, melt spinning is used to spin the masterbatch to obtain nascent fibers. Step 2: The nascent fibers are drawn and spun, followed by winding, forming, bundle drawing and heat setting.

[0028] Example 3 A basalt-modified polyester fiber comprising the following raw materials in parts by weight: 95 parts PET chips, 6.5 parts modified basalt fiber additive, 1 part antioxidant 1010, and 2 parts vinyl bis-stearamide; The method for preparing the polyester fiber includes the following steps: The first step is to add the raw materials measured by weight into a high-speed mixer, control the speed to 300 r / min, and mechanically mix for 1 hour. Then, transfer the mixture to a twin-screw extruder and form masterbatch through melt extrusion. Next, the masterbatch is spun into nascent fibers using melt spinning. Step 2: The nascent fibers are drawn and spun, followed by winding, forming, bundle drawing and heat setting.

[0029] Comparative Example 1 A polyester fiber, which differs from Example 2 in that the modified basalt fiber additive is replaced with basalt fiber, otherwise it is the same.

[0030] Comparative Example 2 A polyester fiber, which differs from Example 2 in that the modified basalt fiber additive is removed, but otherwise it is the same.

[0031] Test case (1) Mechanical properties were tested according to standard GB / T 14344-2008; (2) Flame retardant performance test shall be conducted in accordance with standard FZ / T 50016-2023; The test results are recorded in Table 1: Table 1 - Test Results

[0032] Analysis of the test results shows that the polyester fiber prepared in the embodiments of the present invention has good mechanical properties and flame retardant properties. After replacing the modified basalt fiber additive with basalt fiber, on the one hand, there is a dispersibility problem between it and PET, making it difficult to disperse evenly and play an efficient role. Therefore, the reinforcing effect is limited. However, compared with the polyester fiber made without the addition of basalt fiber, it can still play a certain reinforcing effect. On the other hand, the flame retardant effect of the polymer modifier is lost, and the flame retardant performance of the fiber is greatly reduced.

[0033] This document uses specific examples to illustrate the principles and implementation methods of the present invention. The descriptions of these embodiments are merely to aid in understanding the method and core ideas of the present invention, including the best mode, and to enable any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from its principles, and these improvements and modifications also fall within the scope of protection of the claims. The scope of protection of this patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements similar to those expressed in the claims, or if they include equivalent structural elements that are not substantially different from those expressed in the claims, then these other embodiments should also be included within the scope of the claims.

[0034] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A basalt-modified polyester fiber, characterized in that, Includes the following raw materials measured in parts by weight: 75-95 parts PET chips, 3-6.5 parts modified basalt fiber additive, 0.5-1 part antioxidant, and 1-2 parts vinyl bis-stearamide; The modified basalt fiber additive is basalt fiber with a surface modified by a polymer modifier.

2. The basalt-modified polyester fiber according to claim 1, characterized in that, The modified basalt fiber additive is prepared using the following method: Step 1: Use silane-based surface modifiers to modify the surface of basalt fibers to obtain organic functionalized basalt fibers; Step 2: In a dimethyl sulfoxide medium, using the organic functional groups of the organically functionalized basalt fiber as active initiation sites, functional monomers and chain extenders are polymerized in situ on the surface of the basalt fiber under the action of a catalyst to obtain modified basalt fiber additives.

3. The basalt-modified polyester fiber according to claim 2, characterized in that, In step one, the silane-based surface modifier is 3-glycidyl etheroxypropyltrimethoxysilane or 3-glycidyl etheroxypropyltriethoxysilane.

4. The basalt-modified polyester fiber according to claim 2, characterized in that, In step two, the catalyst is a boron trifluoride diethyl ether complex.

5. The basalt-modified polyester fiber according to claim 2, characterized in that, In step two, the functional monomer is prepared by reacting 5-norbornene-2,2-diethanol and 5,5-dimethyl-1,3,2-dioxophosphanecyclohexane-2-one as raw materials under the action of an accelerator.

6. The basalt-modified polyester fiber according to claim 5, characterized in that, The molar ratio of 5-norbornene-2,2-diethanol and 5,5-dimethyl-1,3,2-dioxophosphanecyclohexane-2-one is 1:

1.

7. The basalt-modified polyester fiber according to claim 5, characterized in that, The accelerator is azobisisobutyronitrile.

8. The basalt-modified polyester fiber according to claim 2, characterized in that, The chain extender monomer is 1,1,3,3-tetramethyl-1,3-bis-[2-[7-oxybicyclo[4.1.0]hept-3-yl]ethyl]disiloxane.

9. A basalt-modified polyester fiber according to claim 1, characterized in that, The antioxidant is any one of antioxidant 168, antioxidant 1076, antioxidant 626, or antioxidant 1010.

10. A method for preparing basalt-modified polyester fiber as described in claim 1, characterized in that, Includes the following steps: The first step is to add the raw materials measured by weight into a high-speed mixer, control the speed to 200-300 r / min, and mechanically mix for 1-2 hours. Then, transfer the mixture to a twin-screw extruder and melt extrusion to form masterbatch. Next, melt spinning is used to spin the masterbatch to obtain nascent fibers. Step 2: The nascent fibers are drawn and spun, followed by winding, forming, bundle drawing and heat setting.

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