阅读说明：本技术 一种高性能直接无捻粗纱的制备方法 (Preparation method of high-performance direct twistless roving ) 是由 崔宝山 杜照孔 于 2021-07-09 设计创作，主要内容包括：本发明公开了一种高性能直接无捻粗纱制备方法,属于无机非金属材料技术领域。上述高性能直接无捻粗纱的制备方法,包括：按比例称取原料,投入玻璃熔炉内,进行玻璃化、熔融处理,然后进行纺丝成型,得到玻璃纤维,冷却后涂覆浸润剂,然后再由直接无捻粗纱拉丝机绕制成高性能直接无捻粗纱并干燥即可。本发明通过对玻璃纤维原料的限定,以及涂覆的浸润剂成分的限定,成功得到断裂强度和拉挤棒材弯曲强度高,毛羽量少的高性能直接无捻粗纱。(The invention discloses a preparation method of high-performance direct twistless roving, and belongs to the technical field of inorganic nonmetallic materials. The preparation method of the high-performance direct twistless roving comprises the following steps: weighing raw materials according to a proportion, putting the raw materials into a glass melting furnace, carrying out vitrification and melting treatment, then carrying out spinning forming to obtain glass fibers, coating a sizing agent after cooling, then winding the glass fibers into high-performance direct twistless roving by a direct twistless roving drawing machine, and drying the high-performance direct twistless roving. According to the invention, through the limitation of the glass fiber raw material and the limitation of the components of the coated sizing agent, the high-performance direct twistless roving with high breaking strength, high bending strength of the pultruded bar and small hairiness is successfully obtained.)

1. A method of making a high performance direct twistless roving, comprising: weighing raw materials in proportion, putting the raw materials into a glass melting furnace, carrying out vitrification and melting treatment, then carrying out spinning forming to obtain glass fibers, coating a sizing agent after cooling, then winding the glass fibers into high-performance direct twistless roving by a direct twistless roving drawing machine, and drying the high-performance direct twistless roving; wherein:

the impregnating compound comprises the following components in parts by weight: 5-10 parts of a silane coupling agent; 10-20 parts of unsaturated polyester resin emulsion; 10-20 parts of water-based epoxy resin emulsion; 1-10 parts of a surfactant; 1-5 parts of a pH regulator; 50-80 parts of deionized water; the silane coupling agent is a mixture of aniline methyl triethoxysilane and divinyl triamino propyl triethoxysilane in a mass ratio of 1: 1; the surfactant is a mixture of fatty alcohol-polyoxyethylene ether and ricinoleic acid ethylene glycol diester sodium sulfate in a mass ratio of 1: 0.4.

2. The method of making high performance direct twistless roving of claim 1, wherein said starting material comprises the following components in weight percent:

the R is₂O is Na₂O、K₂O and Li₂A mixture of O; wherein K₂O stands for R₂5-10% of total weight of O and Na₂O and Li₂The weight ratio of O is 1: 3;

the CaO and Al₂O₃The weight ratio of (1: 1) - (1.75); the weight ratio of SrO to PbO is 2-8: 1.

3. The method of making high performance direct twistless roving of claim 2, wherein said starting material comprises the following components in weight percent:

4. method for producing high-performance direct twistless rovings according to claim 2 or 3, wherein the CaO and Al are₂O₃The weight ratio of (1: 1) - (1.4); the weight ratio of SrO to PbO is 2-5: 1.

5. The method of making high performance direct twistless roving of claim 4, wherein said pH adjusting agent is citric acid.

Technical Field

The invention relates to the technical field of inorganic non-metallic materials, in particular to a preparation method of high-performance direct twistless roving.

Background

Glass fiber (Fiberglass) is an inorganic non-metallic material with excellent performance, has good insulativity, strong heat resistance, good corrosion resistance and high mechanical strength, but is brittle and has poor wear resistance. The hair-care fiber is made of six kinds of ores of pyrophyllite, quartz sand, limestone, dolomite, borocalcite and boromagnesite through the processes of high-temperature melting, wire drawing, winding, weaving and the like, wherein the diameter of each monofilament ranges from several micrometers to twenty micrometers, the monofilament is equivalent to 1/20-1/5 of one hair, and each bundle of fiber precursor consists of hundreds of even thousands of monofilaments. Glass fibers are generally used as reinforcing materials, electrical insulating materials, thermal insulating materials, circuit boards and other inorganic fiber reinforcing materials in composite materials in various fields of national economy, and are the most used inorganic fiber reinforcing materials at present.

The glass fiber direct roving is widely applied to the fields of shipbuilding, wind power blades, petrochemical industry, architectural decoration, heat preservation, heat insulation and the like. Conventional glass fibers are often brittle without surface treatment, and the surface of the glass fibers is often coated with a sizing agent to improve the performance of the glass fibers. The properties of the glass fibers and the special sizing agent are the main influencing factors for improving the properties of the prepared direct roving.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a preparation method of high-performance direct twistless roving; the invention utilizes the specific glass fiber composition, has higher elastic modulus and tensile bending strength on the basis of ensuring better stability, and obtains high-performance direct twistless roving with less hairiness after being treated by special impregnating compound.

In order to solve the technical problems, the invention provides the following technical scheme:

in one aspect, the present invention provides a method of making a high performance direct twistless roving, comprising: weighing raw materials in proportion, putting the raw materials into a glass melting furnace, carrying out vitrification and melting treatment, then carrying out spinning forming to obtain glass fibers, coating a sizing agent after cooling, then winding the glass fibers into high-performance direct twistless roving by a direct twistless roving drawing machine, and drying the high-performance direct twistless roving; wherein:

the impregnating compound comprises the following components in parts by weight: 5-10 parts of a silane coupling agent; 10-20 parts of unsaturated polyester resin emulsion; 10-20 parts of water-based epoxy resin emulsion; 1-10 parts of a surfactant; 1-5 parts of a pH regulator; 50-80 parts of deionized water; the silane coupling agent is a mixture of aniline methyl triethoxysilane and divinyl triamino propyl triethoxysilane in a mass ratio of 1: 1; the surfactant is a mixture of fatty alcohol-polyoxyethylene ether and ricinoleic acid ethylene glycol diester sodium sulfate in a mass ratio of 1: 0.4.

Further, the raw materials comprise the following components in percentage by weight:

the R is₂O is Na₂O、K₂O and Li₂A mixture of O; wherein K₂O stands for R₂5-10% of total weight of O and Na₂O and Li₂The weight ratio of O is 1: 3;

the CaO and Al₂O₃The weight ratio of (1: 1) - (1.75); the weight ratio of SrO to PbO is 2-8: 1.

Preferably, the raw materials consist of the following components in percentage by weight:

further, the CaO is mixed with Al₂O₃The weight ratio of (1: 1) - (1.75); the weight ratio of SrO to PbO is 2-8: 1.

Preferably, the CaO is in combination with Al₂O₃The weight ratio of (1: 1) - (1.4); the weight ratio of SrO to PbO is 2-5: 1.

Preferably, the pH adjusting agent is citric acid.

Compared with the prior art, the invention has the following beneficial effects:

firstly, the invention greatly optimizes the glass fiber raw materials, so that the raw materials have synergistic effect, and the prepared direct twistless roving has higher bending breaking strength.

SiO in the invention₂The skeleton body forming the glass is a network forming substance, and SiO is limited for improving the strength of the glass fiber and ensuring the chemical stability₂The content is higher.

Al₂O₃The addition of (2) has an influence on the crystallization tendency, stability and mechanical strength of the glass fiber, and the stability and mechanical strength of the glass fiber can be improved when the addition amount is higher, but the crystallization rate is increased, the melting difficulty is improved, the viscosity is increased, and the difficulty in the glass melting process is increased.

In order to adjust the viscosity of the glass and the crystallization of the glass, certain content of CaO and MgO is added, and CaO and Al are subjected to crystallization₂O₃The weight ratio of (a) to (b), reducing the viscosity of the glass; meanwhile, the weight ratio of SrO to PbO is limited in the invention, so that the melting temperature of the glass can be reduced, and the strength can be improved to a certain extent. Further, Yb₂O₃BaO and the like are good fluxes, and can reduce the difficulty in melting to some extent.

The invention is on SiO₂And Al₂O₃In the formed network, various ions are introduced, and the addition amount of each substance is limited, especially CaO and Al₂O₃And the weight ratio of SrO to PbO, and the synergistic effect of ions are utilized, so that the prepared high-performance direct twistless roving has higher breaking strength.

Meanwhile, the impregnating compound is prepared by using the silane coupling agent, the unsaturated polyester resin emulsion, the water-based epoxy resin emulsion and the surfactant, so that the breaking strength of the prepared high-performance direct twistless roving can be improved, a raw material guarantee is provided for a glass fiber textile product with high requirements, the performance of the glass fiber direct twistless roving can be improved, the amount of hairiness generated by weaving is less, the breaking strength of the high-performance direct twistless roving is higher, and the high-performance direct twistless roving has better production performance and application performance.

Detailed Description

In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.

In the present invention, the materials and reagents used are not specifically described, and are commercially available.

The invention provides a preparation method of high-performance direct twistless roving, and specific examples are as follows.

Example 1

A method for preparing high-performance direct twistless roving comprises the following steps: raw materials are weighed according to the formula of example 1 in the table 1, put into a glass melting furnace, vitrified and melted, and then spun and molded to obtain the glass fiber. The fiber forming temperature of the glass fiber is 1320-. After cooling, coating the impregnating compound, then winding the mixture into high-performance direct roving by a direct roving drawing machine, and drying the high-performance direct roving at 110 ℃; wherein: the using amount of the impregnating compound is 0.1 percent of the weight of the glass fiber; and the amounts of the components of the impregnating compound are shown in example 1 in Table 2. And the prepared high-performance direct twistless roving is subjected to performance detection, and the result is shown in table 3.

Examples 2 to 7

The raw materials are weighed according to the formulas of the examples 2 to 7 in the table 1, the dosage of each component of the impregnating compound is respectively shown in the examples 2 to 7 in the table 2, and the rest conditions are the same as the example 1.

To further illustrate the beneficial effects of the present invention, a comparative example was constructed as follows, using example 7 as an example only, for reasons of space.

Comparative example 1

The formulation of the impregnating compound was the same as in example 7 except that PbO was replaced with ZnO of the same amount, and the other conditions were the same as in example 7.

Comparative example 2

The formulation of the impregnating compound was the same as in example 7 except that SrO was replaced with the same amount of ZnO, and the other conditions were the same as in example 7.

Comparative example 3

Yb of₂O₃Replaced by the same amount of La₂O₃The formulation of the sizing agent was the same as in example 7, and the other conditions were the same as in example 7.

Comparative example 4

Yb of₂O₃Is replaced by equal amount of Y₂O₃The formulation of the sizing agent was the same as in example 7, and the other conditions were the same as in example 7.

Comparative example 5

Yb of₂O₃Replacement by equal amounts of Fe₂O₃The formulation of the sizing agent was the same as in example 7, and the other conditions were the same as in example 7.

Comparative examples 6 to 9

The raw materials were weighed according to the formulations of comparative examples 6 to 9 in Table 1, the formulation of the impregnating agent was the same as that of example 7, and the other conditions were the same as that of example 7.

2400Tex high-performance direct twistless rovings are produced in the examples and the comparative examples of the invention, the hairiness amount generated by a certain amount of high-performance direct twistless rovings in the manufacturing process is measured, and the breaking strength of the high-performance direct twistless rovings is tested according to GB/T7690.3-2001. And the high-performance direct twistless roving prepared in the examples and the comparative examples is used for reinforcing the performance test of the unsaturated polyester resin pultruded rods with the diameter of 6 mm.

The high performance direct twistless rovings prepared in examples 1-7 were tested for performance and the results are shown in table 3. The high performance direct twistless rovings prepared in comparative examples 1-9 were tested for performance and the results are shown in table 4.

TABLE 1

TABLE 2

The high performance direct twistless rovings prepared in examples 1-7 were tested for performance and the results are shown in table 3. The high performance direct twistless rovings prepared in comparative examples 1-9 were tested for performance and the results are shown in table 4.

TABLE 3

From tables 1-3, it can be seen that a plurality of ions are introduced into the network formed by SiO2 and Al2O3, and the prepared high-performance direct twistless roving has higher breaking strength and bending strength of the pultruded bar by utilizing the synergistic effect between the ions and selecting the specific impregnating compound component, and meanwhile, the hairiness amount is less in the spinning process. TABLE 4

Serial number	Amount of feather mg/kg	Breaking strength N/Tex	Bending strength MPa of pultruded bar
				Comparative example 1	0.62	70.4	1284
Comparative example 2	0.64	71.6	1306
				Comparative example 3	0.57	74.2	1253
Comparative example 4	0.59	71.3	1267
				Comparative example 5	0.67	65.6	1294
Comparative example 6	0.53	67.9	1302
				Comparative example 7	0.54	66.7	1317
Comparative example 8	0.55	62.5	1352
				Comparative example 9	0.54	61.4	1365

As is clear from tables 1 to 4, Yb in the present invention was compared with comparative examples 1 to 5₂O₃Respectively replaced by La₂O₃Or Y₂O₃、Ce₂O₃Replacing ZnO by PbO or SrO, or replacing Yb by Yb₂O₃Substitution of La₂O₃、Y₂O₃Or Fe₂O₃The resulting composition had a relatively low breaking strength and a relatively low flexural strength of the pultruded rods as compared to the examples. This is probably because Pb and Sr can be better introduced into SiO on the basis of the high-content silicon dioxide of the invention₂And Al₂O₃The formed network and the large ionic radius of Yb ions act together, and can be well fixed in the network, so that the ions are prevented from moving in the network, and the network has higher elastic modulus and higher tensile strength.

As can be seen from the data in Table 3, the direct twistless rovings obtained in different ratio ranges have larger difference between the breaking strength and the bending strength of the pultruded rods than the comparative examples 4 to 7, while the CaO/Al in the specific ratio range of the present invention₂O₃MgO and Ce₂O₃/Yb₂O₃In a weight ratio of (A) and R₂Li in O₂And the dosage proportion of O can obtain the direct twistless roving with the breaking strength and the bending strength of the pultruded bar.

In comparative examples 6 to 9, CaO/Al was adjusted₂O₃、PbO/SrO、K₂The amount of O is adjusted to Na₂O/Li₂The proportion of O is not within the protection range of the invention, and the obtained high-performance direct twistless roving has the breaking strength and the pultrusion rodThe difference in the bending strength of the materials is large because of the CaO/Al ratio in a specific range₂O₃And PbO/SrO are cooperated, so that the viscosity of glass in the melting process can be reduced, and the direct twistless roving with the breaking strength and the bending strength of the pultruded bar can be obtained.

The special sizing agent has good permeability, and can form a good coating film on the surface of the glass fiber to prevent hairiness in the spinning process.

In conclusion, the invention successfully obtains the high-performance direct twistless roving with high breaking strength, high bending strength of the pultruded bar and less hairiness by limiting the glass fiber raw material and the components of the coated sizing agent.

The foregoing is a preferred embodiment of the present invention, and it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and are intended to be within the scope of the invention.