CN112979185B - Glass fiber impregnating compound and preparation method thereof - Google Patents

Abstract

The invention discloses a glass fiber impregnating compound and a preparation method thereof, and belongs to the technical field of impregnating compounds. The glass fiber impregnating compound comprises the following components in parts by weight: 10-20 parts of a silane coupling agent; 20-40 parts of unsaturated polyester resin emulsion; 10-20 parts of water-based epoxy resin emulsion; 1-10 parts of a surfactant; 1-10 parts of a pH regulator; 1-5 parts of an antistatic agent; 60-80 parts of deionized water; the silane coupling agent is a mixture of 3-mercaptopropyltrimethoxysilane and gamma-glycidyl ether propyltrimethoxysilane in a mass ratio of 1: 0.4-0.8; the surfactant is a mixture of fatty alcohol-polyoxyethylene ether and sodium stearyl sulfate in a mass ratio of 1: 1-2. The silane coupling agent and the surfactant in a specific ratio in the invention act together with the resin emulsion, so that the prepared reinforced material has better mechanical property and mechanical property.

Description

Glass fiber impregnating compound and preparation method thereof

Technical Field

The invention relates to the technical field of impregnating compounds, in particular to a glass fiber impregnating compound and a preparation method thereof.

Background

The Ministry of industry and belief requires that the oil consumption reaches the target of 5L/100km in 2020, and about 1/4 enterprises fail to reach the target of the same year in 2015, the Ministry of industry and belief penalizes the enterprises in a plurality of ways such as not accepting new product declaration and not accepting unqualified enterprise investment projects. At present, the pressure of energy conservation and consumption reduction of automobile manufacturers is high, and the light weight of automobiles is an important way for realizing energy conservation and consumption reduction.

The light weight of the automobile is a concern for both consumers and vehicle enterprises, and the selection of materials is very critical in order to achieve the goal of light weight, besides the optimization of structure and process design. In order to reduce the weight of the automobile, a large amount of engineering plastics, particularly glass fiber reinforced plastics are adopted for the automobile enterprises, and the glass fiber reinforced plastics are used for replacing traditional high-strength steel, magnesium-aluminum alloy and the like, so that the weight of the automobile can be reduced to a greater extent, the energy is saved, the consumption is reduced, and the manufacturing cost is also saved. But different fiber materials are needed to be utilized for different resin matrixes, so that a better effect can be achieved.

The composition and preparation process of the conventional glass fiber raw material are quite mature and difficult to change. But the compatibility of the pure glass fiber and the resin matrix is poor, so that the surface performance of the glass fiber can be changed by using the impregnating compound, the compatibility of the glass fiber and the resin matrix is enhanced, and the performance of the composite material is improved to a certain extent. For example, patents CN107540244A, CN108640535A, CN108996923A, etc. all improve the surface properties of glass fibers by using wetting agents, and further improve the properties of reinforced plastics.

In the production process of glass fibers, the surface of the glass fibers needs to be coated with the impregnating compound, the quality of the glass fibers is determined to a great extent by the performance of the impregnating compound, and the impregnating compound can enhance the adhesion, the raising resistance and the coating property of fiber bundles, so that the surfaces of the fibers are smooth, the wear resistance and the flexibility are improved, the fibers are easy to wind, and the damage is reduced during winding; and the compatibility of the glass fiber and the resin matrix can be improved, so that the mechanical property of the prepared composite material is improved. However, the existing impregnating compound has slow permeation on the surface of the glass fiber and poor film forming property, so that the prepared composite material has poor mechanical property and is inconvenient to apply.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a glass fiber impregnating compound and a preparation method thereof; the sizing agent has good compatibility with resin, and the silane coupling agent with specific composition and proportion ensures that the glass fiber and the resin matrix have better adhesion, and the glass fiber reinforced resin composite material prepared by the sizing agent has good mechanical property and mechanical property.

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

on one hand, the invention provides a glass fiber impregnating compound, which consists of the following components in parts by weight:

10-20 parts of a silane coupling agent;

20-40 parts of unsaturated polyester resin emulsion;

10-20 parts of water-based epoxy resin emulsion;

1-10 parts of a surfactant;

1-10 parts of a pH regulator;

1-5 parts of an antistatic agent;

60-80 parts of deionized water;

the silane coupling agent is a mixture of 3-mercaptopropyltrimethoxysilane and gamma-glycidyl ether propyltrimethoxysilane in a mass ratio of 1: 0.4-0.8;

the surfactant is a mixture of fatty alcohol-polyoxyethylene ether and sodium stearyl sulfate in a mass ratio of 1: 1-2.

Preferably, the glass fiber sizing agent consists of the following components in parts by weight:

10-15 parts of a silane coupling agent;

25-35 parts of unsaturated polyester resin emulsion;

10-15 parts of water-based epoxy resin emulsion;

5-10 parts of a surfactant;

1-5 parts of a pH regulator;

2-5 parts of an antistatic agent;

60-80 parts of deionized water.

Further, the molecular weight of the unsaturated polyester resin emulsion is 800-3000; the molecular weight of the aqueous epoxy resin emulsion is 300-500.

Preferably, the antistatic agent is ammonium chloride or an ethoxylated alkyl amine.

Preferably, the pH regulator is citric acid and/or acetic acid.

On the other hand, the invention also provides a preparation method of the glass fiber impregnating compound, which comprises the following steps:

step 1: dissolving a surfactant in a part of deionized water, and then adding a silane coupling agent and uniformly mixing;

step 2: diluting the unsaturated polyester resin emulsion and the waterborne epoxy resin emulsion with the rest deionized water respectively, adding the diluted unsaturated polyester resin emulsion and the diluted waterborne epoxy resin emulsion into the mixed solution obtained in the step (1), and uniformly mixing;

and step 3: and (3) adding a pH regulator and an antistatic agent into the solution obtained in the step (2), and uniformly mixing to obtain the impregnating compound.

In another aspect, the invention further provides an application of the glass fiber sizing agent, wherein the glass fiber sizing agent is diluted to form a 5-10wt% aqueous solution, and the glass fiber is coated.

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

in the invention, the silane coupling agent is 3-mercaptopropyltrimethoxysilane and gamma-glycidyl ether propyltrimethoxysilane in a specific ratio, a reaction group generated after hydrolysis can react with silicon dioxide in the glass fiber, and a mercapto group and an epoxyalkyl group at the other end can be combined with a resin matrix, so that the glass fiber and the resin matrix have better compatibility.

Meanwhile, the silane coupling agent and the resin emulsion can be well dispersed through the surfactant, the resin emulsion can be quickly soaked when contacting with the glass fiber, a uniform resin emulsion film is formed on the surface of the glass fiber, the compatibility of the glass fiber and a resin matrix is improved, and the prepared reinforced material has good mechanical property and mechanical property.

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 glass fiber impregnating compound and a preparation method thereof, and the specific embodiment is as follows.

Example 1

A method for preparing a glass fiber sizing, the amounts of the materials are shown in table 1, the data of example 1, and the method comprises the following steps:

step 1: dissolving a surfactant in 1/2 deionized water, and then adding a silane coupling agent and uniformly mixing;

step 2: diluting the unsaturated polyester resin emulsion and the waterborne epoxy resin emulsion with the rest deionized water respectively, adding the diluted unsaturated polyester resin emulsion and the diluted waterborne epoxy resin emulsion into the mixed solution obtained in the step (1), and uniformly mixing;

and step 3: and (3) adding a pH regulator and an antistatic agent into the solution obtained in the step (2), and uniformly mixing to obtain the impregnating compound.

The molecular weight of the unsaturated polyester resin emulsion is 800-3000; the molecular weight of the aqueous epoxy resin emulsion is 300-500.

Preferably, the silane coupling agent is a mixture of 3-mercaptopropyltrimethoxysilane and gamma-glycidyl ether propyl-trimethoxysilane;

the surfactant is a mixture of fatty alcohol-polyoxyethylene ether and sodium octadecyl sulfate;

the antistatic agent is ammonium chloride or ethoxylated alkyl amine; the pH regulator is citric acid and/or acetic acid.

Examples 2 to 6

The contents of the respective substances are shown as data in examples 2 to 6 in Table 1, respectively, and the other conditions are the same as in example 1.

To further illustrate the beneficial effects of the present application, a comparative example was constructed as follows, using example 3 as an example only, for reasons of space.

Comparative example 1

The same conditions as in example 3 were followed except that 3-mercaptopropyltrimethoxysilane was replaced with the same amount of gamma-glycidoxypropyltrimethoxysilane.

Comparative example 2

The same conditions as in example 3 were followed except that gamma-glycidoxypropyltrimethoxysilane was replaced with the same amount of 3-mercaptopropyltrimethoxysilane.

Comparative example 3

The same procedure as in example 3 was repeated except that 3-mercaptopropyltrimethoxysilane was replaced with the same amount of gamma-aminopropyltriethoxysilane.

Comparative example 4

The same conditions as in example 3 were followed except that 3-mercaptopropyltrimethoxysilane was replaced with the same amount of gamma- (methacryloyloxy) propyltrimethoxysilane.

Comparative example 5

The same procedure as in example 3 was repeated except that 3-mercaptopropyltrimethoxysilane was replaced with the same amount of gamma- (methacryloyloxy) propyltrimethoxysilane and gamma-glycidoxypropyltrimethoxysilane was replaced with the same amount of gamma-aminopropyltriethoxysilane.

Comparative example 6

The same procedure as in example 3 was repeated except that the fatty alcohol-polyoxyethylene ether was replaced with the same amount of sodium stearyl sulfate.

Comparative example 7

The same procedure as in example 3 was repeated except that the sodium stearyl sulfate was replaced with the same amount of fatty alcohol-polyoxyethylene ether.

Comparative example 8

The sodium octadecyl sulfate was replaced with an equal amount of quaternary ammonium bromide salt of a fatty acid, and the remaining conditions were the same as in example 3.

Comparative example 9

The surfactant was omitted and the remaining conditions were the same as in example 3.

Comparative example 10

The mass ratio of 3-mercaptopropyltrimethoxysilane to gamma-glycidoxypropyltrimethoxysilane was 1:1, and the other conditions were the same as in example 3.

Comparative example 11

The mass ratio of 3-mercaptopropyltrimethoxysilane to gamma-glycidoxypropyltrimethoxysilane was 1:0.2, and the other conditions were the same as in example 3.

TABLE 1

Respectively preparing glass fibers by using the impregnating compounds of the embodiment and the comparative example, diluting the impregnating compounds into 10wt% aqueous solution, drawing 5000 holes of 2000tex protofilament, drying at 130 ℃ for 14h, fully opening the microwave, coating the impregnating compounds, and adding the impregnating compound solution with the amount of 0.1% of the weight of the glass fibers to prepare the composite material, wherein the content of the glass fibers is 16%. The polystyrene composites of each example and comparative example were tested for tensile strength and elongation at break, respectively, according to the test standard ASTM/D638; and tested for flexural strength, test standard ASTM/D790. Examples 1-6 the impregnating compounds were used to prepare glass fiber reinforced polystyrene composites for performance and the results are shown in Table 2. Comparative examples 1-11 impregnating compounds were used to prepare glass fiber reinforced polystyrene composites, and the results are shown in Table 3.

TABLE 2

As shown in Table 2, the composite material obtained by using the glass fiber prepared by the impregnating compound of the present invention as the reinforcing material of polystyrene has a higher tensile breaking strength, which is increased by 1.37 times compared with the tensile breaking strength of the polystyrene material itself of 35MPa, and the bending strength of the polystyrene material itself of 48MPa, which is increased by more than 0.87 times.

TABLE 3

As can be seen from tables 1 to 3, by changing the kinds and the ratio of the silane coupling agent in the present invention, the properties of the composite material prepared according to the present invention are reduced, compared to comparative examples 1 to 5 and comparative examples 10 to 11, which is probably because the present invention selects 3-mercaptopropyltrimethoxysilane and gamma-glycidoxypropyltrimethoxysilane in specific ratios, so that the glass fiber has better compatibility with the resin matrix.

Compared with the comparative examples 6 to 9, by changing the kind of the surfactant in the present invention, the properties of the composite material prepared were also reduced in all aspects. The silane coupling agent and the resin emulsion can be well dispersed through the specific surfactant, the resin emulsion can be quickly soaked when contacting with the glass fiber, a uniform resin emulsion film is formed on the surface of the glass fiber, the compatibility of the glass fiber and a resin matrix is improved, and the prepared reinforced material has good mechanical property and mechanical property.

In conclusion, the 3-mercaptopropyltrimethoxysilane, the gamma-glycidyl ether propyl trimethoxysilane and the surfactant in a specific ratio in the invention act together with the resin emulsion, so that the glass fiber and the resin matrix have good compatibility, and the prepared reinforcing material has good mechanical property and mechanical property.

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.

Claims (6)

1. The glass fiber impregnating compound is characterized by comprising the following components in parts by weight:

8.3 parts of 3-mercaptopropyl trimethoxy silane;

6.7 parts of gamma-glycidyl ether propyl trimethoxy silane;

30 parts of unsaturated polyester resin emulsion;

12 parts of water-based epoxy resin emulsion;

1.7 parts of fatty alcohol-polyoxyethylene ether;

3.3 parts of sodium octadecyl sulfate;

5 parts of a pH regulator;

3 parts of an antistatic agent;

80 parts of deionized water.

2. The glass fiber sizing agent according to claim 1, wherein the molecular weight of said unsaturated polyester resin emulsion is 800-3000; the molecular weight of the aqueous epoxy resin emulsion is 300-500.

3. A glass fiber sizing composition according to claim 1, wherein said antistatic agent is ammonium chloride or ethoxylated alkyl amine.

4. The glass fiber sizing agent according to claim 1, wherein said pH adjusting agent is citric acid and/or acetic acid.

5. A method for preparing a glass fiber sizing agent according to any one of claims 1 to 4, characterized by comprising:

step 1: dissolving fatty alcohol-polyoxyethylene ether and sodium octadecyl sulfate in a part of deionized water, and then adding 3-mercaptopropyl trimethoxy silane and gamma-glycidyl ether propyl trimethoxy silane to mix uniformly;

step 2: diluting the unsaturated polyester resin emulsion and the waterborne epoxy resin emulsion with the rest deionized water respectively, adding the diluted unsaturated polyester resin emulsion and the diluted waterborne epoxy resin emulsion into the mixed solution obtained in the step (1), and uniformly mixing;

and step 3: and (3) adding a pH regulator and an antistatic agent into the solution obtained in the step (2), and uniformly mixing to obtain the impregnating compound.

6. The use of a glass fiber sizing agent according to any one of claims 1 to 4, wherein said sizing agent is diluted to form a 5-10wt% aqueous solution, and the glass fiber is coated.