阅读说明：本技术 低气味玻璃纤维浸润剂及其制备方法和应用 (Low-odor glass fiber impregnating compound and preparation method and application thereof ) 是由 徐永军 申玉亭 王帅 贾婧婧 于 2021-01-06 设计创作，主要内容包括：本发明属于浸润剂技术领域,具体涉及一种低气味玻璃纤维浸润剂及其制备方法和应用。低气味玻璃纤维浸润剂是由偶联剂、润滑剂、成膜剂A、成膜剂B和去离子水组成,其中,成膜剂A为马来酸酐改性聚丙烯蜡乳液,成膜剂B为聚乙酸乙烯脂乳液。本发明使用偶联剂可以保证后续产品的性能；使用PE蜡乳液作为润滑剂,大大降低玻纤气味；选用搭配成膜剂保证玻纤在LFT后续的工艺性,以及成膜剂选择根据相似相溶原理与聚丙烯树脂有更好的界面相容性,同时考虑气味的来源给予规避,也起到降低气味效果。(The invention belongs to the technical field of impregnating compounds, and particularly relates to a low-odor glass fiber impregnating compound and a preparation method and application thereof. The low-odor glass fiber impregnating compound consists of a coupling agent, a lubricant, a film forming agent A, a film forming agent B and deionized water, wherein the film forming agent A is maleic anhydride modified polypropylene wax emulsion, and the film forming agent B is polyvinyl acetate emulsion. The coupling agent is used in the invention, so that the performance of subsequent products can be ensured; the PE wax emulsion is used as a lubricant, so that the smell of glass fibers is greatly reduced; the selected film agent ensures the subsequent manufacturability of the glass fiber in LFT, and the film agent has better interface compatibility with the polypropylene resin according to the similar intermiscibility principle, and simultaneously, the odor source is considered to avoid, thereby playing the role of reducing the odor.)

1. The low-odor glass fiber impregnating compound is characterized by consisting of a coupling agent, a lubricating agent, a film forming agent A, a film forming agent B and deionized water, wherein the film forming agent A is maleic anhydride modified polypropylene wax emulsion, and the film forming agent B is polyvinyl acetate emulsion.

2. The low-odor glass fiber sizing agent as claimed in claim 1, wherein said coupling agent is an aminosilane-based coupling agent.

3. The low odor glass fiber sizing composition as defined in claim 1, wherein said lubricant is a PE wax emulsion.

4. The low-odor glass fiber sizing agent as claimed in claim 1, wherein the total mass of said coupling agent, said lubricant, said film-forming agent a and said film-forming agent B is 2-4% of the total mass of the low-odor glass fiber sizing agent.

5. The low-odor glass fiber sizing agent as set forth in claim 1, wherein the amount of the coupling agent, the lubricant, the film-forming agent A and the film-forming agent B is 100% by mass,

6. the low-odor glass fiber sizing agent as claimed in claim 1, wherein the mass ratio of the film forming agent A to the film forming agent B is 1.25-8.5: 1.

7. A method for preparing a low-odor glass fiber sizing agent as defined in any one of claims 1 to 6, comprising the steps of:

(1) adding a coupling agent into deionized water, and stirring;

(2) diluting the lubricant with deionized water, adding the diluted lubricant and stirring the diluted lubricant;

(3) diluting the film forming agent A with deionized water, adding and stirring;

(4) diluting the film forming agent B with deionized water, adding and stirring;

(5) and adding the rest deionized water to obtain the low-odor glass fiber impregnating compound.

8. The method according to claim 7, wherein the amount of deionized water added in step (1) is 30-40% of the total mass of the low-odor glass fiber sizing.

9. The method for preparing a low-odor glass fiber sizing agent as claimed in claim 7, wherein the mass of the deionized water in the step (2) is 3-5 times of the mass of the lubricant;

the mass of the deionized water in the step (3) is 2-3 times of that of the film forming agent A;

the mass of the deionized water in the step (4) is 2-3 times of that of the film forming agent B.

10. Use of a low-odor glass fiber sizing composition as defined in any one of claims 1 to 6, wherein the low-odor glass fiber sizing composition is used for producing alkali-free glass fibers for LFT-reinforced polypropylene.

Technical Field

The invention belongs to the technical field of impregnating compounds, and particularly relates to a low-odor glass fiber impregnating compound and a preparation method and application thereof.

Background

LFT (long Fiber reinforced thermoplastics), which is a composite material for long glass Fiber reinforced thermoplastics, has been widely used in recent years for processing automobile parts, including front end modules, automobile interior panels, instrument panels, automobile tail doors, sports equipment, transportation, and the like. The glass fiber reinforced composite material produced by the LFT process has longer glass fiber retention length, so that the product has good strength and rigidity. It is noted that for automotive materials, the odor of interior materials or articles is currently limited by various host manufacturers to minimize or improve the unpleasant odor, and not to completely eliminate the odor (that is not possible). According to the investigation, the odor emission of the automobile interior is mainly from various leathers, plastics and the like, wherein the plastics are mainly front end modules, automobile interior panels, instrument panels and the like, and the seats and ceilings (GMT plates) are also one of the main source parts of the odor due to large area and special positions.

The development of environmental protection and light weight of automobiles promotes the application and rapid popularization of low-odor materials in the field of automobiles. Low-odor materials are selected when automobile interior parts are selected, and the low-odor development trend of the LFT composite material which is one of automobile interior parts is obvious. In order to meet the requirement of low odor of automobiles, LFT particle manufacturers continuously optimize and improve resin formula systems. Currently, LFT material suppliers primarily perform odor post-treatment, but still do not fully meet the needs of various automotive manufacturers. Glass fibers are urgently needed to develop towards low odor as LFT reinforcing materials.

Chinese patent CN 111499221A discloses a low-odor glass fiber impregnating compound, a preparation method and application thereof, wherein the impregnating compound contains solid components and water; the mass of the solid component accounts for 2-10% of the total mass of the impregnating compound; the mass of each component of the solid component accounts for the total mass of the solid component, and the mass percentage of each component of the solid component is expressed as follows: 8.0-20% of coupling agent, 4.0-10% of lubricant, 60-85% of film forming agent, 1.0-5.0% of antistatic agent and 0.5-4.0% of pH value regulator; wherein the film forming agent consists of self-emulsifying water-based epoxy resin and self-crosslinking polyvinyl acetate; the mass ratio of the self-emulsifying water-based epoxy resin to the self-crosslinking polyvinyl acetate is 1: 1-3: 1. Although the low-odor glass fiber impregnating compound prepared in the patent can be used for producing glass fiber twisted yarn products, the effect is poor when the low-odor glass fiber impregnating compound is used for producing LFT due to the limitation of a raw material system, and the odor test method in the patent is set by self and is different from the national standard or the standard, and the odor test result is to be further examined.

Therefore, it is highly desirable to provide a low-odor glass fiber impregnating compound for LFT of reinforced polypropylene resin, which not only makes the glass fiber suitable for LFT process, but also has ultra-low odor, and meets the odor requirements of different host factories in the downstream.

Disclosure of Invention

The invention aims to provide a low-odor glass fiber impregnating compound, a glass fiber product produced by using the impregnating compound has lower odor, good compatibility with PP (polypropylene), good manufacturability of LFT (Long fiber reinforced thermoplastic) and good wear resistance, less hairiness and easy dispersion; the invention also provides a preparation method and application of the low-odor glass fiber impregnating compound.

The low-odor glass fiber impregnating compound consists of a coupling agent, a lubricant, a film forming agent A, a film forming agent B and deionized water, wherein the film forming agent A is maleic anhydride modified polypropylene wax emulsion, and the film forming agent B is polyvinyl acetate emulsion.

The coupling agent is amino silane coupling agent.

The lubricant is PE wax emulsion.

The total mass of the coupling agent, the lubricant, the film forming agent A and the film forming agent B is 2-4% of the total mass of the low-odor glass fiber impregnating compound.

Based on the total mass of the coupling agent, the lubricant, the film forming agent A and the film forming agent B as 100 percent,

the following are preferred, based on 100% of the total mass of the coupling agent, the lubricant, the film-forming agent A and the film-forming agent B:

the following is more preferable, based on 100% of the total mass of the coupling agent, the lubricant, the film-forming agent a and the film-forming agent B:

the total mass of the coupling agent, the lubricant, the film forming agent A and the film forming agent B is 100 percent, and the following is preferred:

the mass ratio of the film forming agent A to the film forming agent B is 1.25-8.5: 1.

The preparation method of the low-odor glass fiber impregnating compound comprises the following steps:

(1) adding a coupling agent into deionized water, and stirring;

(2) diluting the lubricant with deionized water, adding the diluted lubricant and stirring the diluted lubricant;

(3) diluting the film forming agent A with deionized water, adding and stirring;

(4) diluting the film forming agent B with deionized water, adding and stirring;

(5) and adding the rest deionized water to obtain the low-odor glass fiber impregnating compound.

The adding amount of the deionized water in the step (1) is 30-40% of the total mass of the low-odor glass fiber impregnating compound.

The mass of the deionized water in the step (2) is 3-5 times of that of the lubricant;

the mass of the deionized water in the step (3) is 2-3 times of that of the film forming agent A;

the mass of the deionized water in the step (4) is 2-3 times of that of the film forming agent B.

The application of the low-odor glass fiber impregnating compound is that the low-odor glass fiber impregnating compound is used for producing alkali-free glass fibers for LFT reinforced polypropylene.

The coupling agent is selected from the group consisting of Mimeji chartA-1387, win Sivo 1208, etc. The reactive group after hydrolysis of the coupling agent,the glass fiber and the matrix resin (polypropylene resin) can be linked to play a role of bridging, so that the bonding property of the glass fiber and the resin can be better improved, and the performance requirement of the final composite material is met. The coupling agent is beneficial to improving the production efficiency of the glass fiber, can reduce the broken fiber of the fiber and ensure the integrity of the fiber, and meanwhile, the coupling agent is mainly beneficial to reducing the using amount of a lubricating agent, reducing the introduced raw materials of smell and ensuring the manufacturability of the subsequent use of the glass fiber; the selection of a proper coupling agent not only meets the performance of LFT reinforced polypropylene, but also meets the production manufacturability.

The lubricant of the present invention is selected to be a PE wax emulsion. The lubricant can reduce the friction force of the glass fiber in the wire drawing and product processing processes, protects the glass fiber from being damaged in the production and subsequent use processes, is a main influence factor of the product in the aspects of the productivity and the use manufacturability, and the reasonable selection of the lubricant is beneficial to improving the manufacturability of the LFT reinforced polypropylene yarn and improving the production efficiency of the glass fiber in the use process. However, the lubricant is generally smelly and cannot be completely removed, and the subsequent product and resin binding property are affected, so that the proper lubricant needs to be selected and the amount of the lubricant needs to be controlled. The lubricant is preferably ML723-NS of Mackerel.

The film forming agent used in the invention is used as a main component of the impregnating compound system, can repair the surface defects of the glass fibers, protects the strand convergence, is a key for influencing the use performance of the glass fibers, provides excellent manufacturability and mechanical performance, and mainly considers the compatibility with the target resin (polypropylene) and the odor. The film forming agent A is modified polypropylene wax emulsion obtained by grafting maleic anhydride and under the alkali neutralization condition, the selected molecular weight of the modified polypropylene wax emulsion is 1-6 ten thousand, and the particle size of emulsion particles is 20-100 nm. The film forming agent B is polyvinyl acetate emulsion. The modified polypropylene wax emulsion can provide a good reaction carrier for glass fibers; and the use of polyvinyl acetate emulsion can provide better bundling nature for glass fiber on the one hand, and on the other hand, can neutralize the alkali in the modified polypropylene wax, consequently adopts modified polypropylene wax emulsion and polyvinyl acetate emulsion collocation to use, can make glass fiber smell reduce, has the manufacturability simultaneously concurrently to make glass fiber can apply to in the LFT production. The film forming agent A is preferably Nippon chemical P-5300, and the film forming agent B is preferably Serania Vinamul 8828.

The combustible content (LOI) of the glass fiber prepared by the low-odor glass fiber impregnating compound is generally controlled to be 0.1-0.5, preferably 0.2-0.4, and the preferred scheme is mainly used as a theoretical reference value of the performance of the composite material of the final product.

The invention has the following beneficial effects:

compared with the prior art, the coupling agent is used in the invention, so that the performance of subsequent products can be ensured; the PE wax emulsion is used as a lubricant, so that the smell of glass fibers is greatly reduced; the selected film agent ensures the subsequent manufacturability of the glass fiber in LFT, and the film agent has better interface compatibility with the polypropylene resin according to the similar intermiscibility principle, and simultaneously, the odor source is considered to avoid, thereby playing the role of reducing the odor.

The glass fiber produced by the impregnating compound can reduce the odor of a final product by over 0.5 (according to the popular PV3900-2000 test standard), and meanwhile, the product meets the production requirement of an LFT process.

Detailed Description

The present invention is further described below with reference to examples.

Example 1

The content of each component of the low-odor glass fiber impregnating compound is shown in table 1, the total mass of the coupling agent, the lubricating agent, the film forming agent A and the film forming agent B is 3% of the total mass of the low-odor glass fiber impregnating compound, and the balance is deionized water.

The coupling agent is a Michael diagramA-1387 silane coupling agent.

The lubricant is ML723-NS of Mackerel.

The film forming agent A is Nippon chemical P-5300.

Film former B was Seranian Vinamul 8828.

The preparation method comprises the following steps:

(1) adding deionized water into a preparation tank until the mass of the deionized water is 30% of the total mass of the low-odor glass fiber impregnating compound, starting a stirrer of the preparation tank, slowly adding a coupling agent, and stirring until a solution is clear and transparent and has no oily residue;

(2) diluting the lubricant with normal-temperature deionized water, adding the diluted lubricant and continuously stirring the diluted lubricant, wherein the mass of the deionized water is 5 times that of the lubricant;

(3) diluting the film forming agent A with normal-temperature deionized water, adding the diluted film forming agent A and continuously stirring the diluted film forming agent A, wherein the mass of the deionized water is 2 times that of the film forming agent A;

(4) diluting the film forming agent B with normal-temperature deionized water, adding the diluted film forming agent B and continuously stirring the diluted film forming agent B, wherein the mass of the deionized water is 2 times that of the film forming agent B;

(5) and adding the rest deionized water to obtain the low-odor glass fiber impregnating compound.

The alkali-free glass fiber for LFT reinforced polypropylene is prepared by adopting the low-odor glass fiber impregnating compound and the conventional method, and the LFT composite material is prepared by adopting the alkali-free glass fiber for LFT reinforced polypropylene and the conventional method.

The detection results of the alkali-free glass fiber and LFT composite material for the prepared LFT reinforced polypropylene are shown in Table 1.

The odor detection is carried out according to the popular PV3900-2000 test standard.

Example 2

The content of each component of the low-odor glass fiber impregnating compound is shown in table 1, the total mass of the coupling agent, the lubricating agent, the film forming agent A and the film forming agent B is 2% of the total mass of the low-odor glass fiber impregnating compound, and the balance is deionized water.

The coupling agent is a Michael diagramA-1387 silane coupling agent.

The lubricant is ML723-NS of Mackerel.

The film forming agent A is Nippon chemical P-5300.

Film former B was Seranian Vinamul 8828.

The preparation method comprises the following steps:

(1) adding deionized water into a preparation tank to 40% of the total mass of the low-odor glass fiber impregnating compound, starting a stirrer of the preparation tank, slowly adding a coupling agent, and stirring until the solution is clear and transparent and has no oily residue;

(2) diluting the lubricant with normal-temperature deionized water, adding the diluted lubricant and continuously stirring the diluted lubricant, wherein the mass of the deionized water is 3 times that of the lubricant;

(3) diluting the film forming agent A with normal-temperature deionized water, adding the diluted film forming agent A and continuously stirring the diluted film forming agent A, wherein the mass of the deionized water is 3 times that of the film forming agent A;

(4) diluting the film forming agent B with normal-temperature deionized water, adding the diluted film forming agent B and continuously stirring the diluted film forming agent B, wherein the mass of the deionized water is 3 times that of the film forming agent B;

(5) and adding the rest deionized water to obtain the low-odor glass fiber impregnating compound.

The alkali-free glass fiber for LFT reinforced polypropylene is prepared by adopting the low-odor glass fiber impregnating compound and the conventional method, and the LFT composite material is prepared by adopting the alkali-free glass fiber for LFT reinforced polypropylene and the conventional method.

The detection results of the alkali-free glass fiber and LFT composite material for the prepared LFT reinforced polypropylene are shown in Table 1.

The odor detection is carried out according to the popular PV3900-2000 test standard.

Example 3

The content of each component of the low-odor glass fiber impregnating compound is shown in table 1, the total mass of the coupling agent, the lubricating agent, the film forming agent A and the film forming agent B is 4% of the total mass of the low-odor glass fiber impregnating compound, and the balance is deionized water.

The coupling agent is a Michael diagramA-1387 silane coupling agent.

The lubricant is ML723-NS of Mackerel.

The film forming agent A is Nippon chemical P-5300.

Film former B was Seranian Vinamul 8828.

The preparation method comprises the following steps:

(1) adding deionized water into a preparation tank until the mass of the deionized water is 35% of the total mass of the low-odor glass fiber impregnating compound, starting a stirrer of the preparation tank, slowly adding a coupling agent, and stirring until a solution is clear and transparent and has no oily residue;

(2) diluting the lubricant with normal-temperature deionized water, adding the diluted lubricant and continuously stirring the diluted lubricant, wherein the mass of the deionized water is 4 times that of the lubricant;

(3) diluting the film forming agent A with normal-temperature deionized water, adding the diluted film forming agent A and continuously stirring the diluted film forming agent A, wherein the mass of the deionized water is 2 times that of the film forming agent A;

(4) diluting the film forming agent B with normal-temperature deionized water, adding the diluted film forming agent B and continuously stirring the diluted film forming agent B, wherein the mass of the deionized water is 3 times that of the film forming agent B;

(5) and adding the rest deionized water to obtain the low-odor glass fiber impregnating compound.

The alkali-free glass fiber for LFT reinforced polypropylene is prepared by adopting the low-odor glass fiber impregnating compound and the conventional method, and the LFT composite material is prepared by adopting the alkali-free glass fiber for LFT reinforced polypropylene and the conventional method.

The detection results of the alkali-free glass fiber and LFT composite material for the prepared LFT reinforced polypropylene are shown in Table 1.

The odor detection is carried out according to the popular PV3900-2000 test standard.

Example 4

The content of each component of the low-odor glass fiber impregnating compound is shown in table 1, the detection results of the alkali-free glass fiber and LFT composite material for the prepared LFT reinforced polypropylene are shown in table 1 in the same way as in example 1, and the odor detection is carried out according to the popular PV3900-2000 test standard.

Example 5

The content of each component of the low-odor glass fiber impregnating compound is shown in table 1, the detection results of the alkali-free glass fiber and LFT composite material for the prepared LFT reinforced polypropylene are shown in table 1 in the same way as in example 1, and the odor detection is carried out according to the popular PV3900-2000 test standard.

Comparative example 1

The content of each component of the glass fiber impregnating compound is shown in table 1, the total mass of the coupling agent, the lubricating agent and the film forming agent A is 3 percent of the total mass of the glass fiber impregnating compound, and the balance is deionized water.

The coupling agent is a Michael diagramA-1387 silane coupling agent.

The lubricant is ML723-NS of Mackerel.

The film forming agent A is Nippon chemical P-5300.

The preparation method comprises the following steps:

(1) adding deionized water into a preparation tank until the mass of the deionized water is 30% of the total mass of the glass fiber impregnating compound, starting a stirrer of the preparation tank, slowly adding a coupling agent, and stirring until the solution is clear and transparent and has no oily residue;

(2) diluting the lubricant with normal-temperature deionized water, adding the diluted lubricant and continuously stirring the diluted lubricant, wherein the mass of the deionized water is 5 times that of the lubricant;

(3) diluting the film forming agent A with normal-temperature deionized water, adding the diluted film forming agent A and continuously stirring the diluted film forming agent A, wherein the mass of the deionized water is 2 times that of the film forming agent A;

(4) diluting the film forming agent B with normal-temperature deionized water, adding the diluted film forming agent B and continuously stirring the diluted film forming agent B, wherein the mass of the deionized water is 2 times that of the film forming agent B;

(5) and adding the rest deionized water to obtain the glass fiber impregnating compound.

The alkali-free glass fiber for LFT reinforced polypropylene is prepared by adopting a glass fiber impregnating compound and a conventional method, and the alkali-free glass fiber for LFT reinforced polypropylene is used for preparing the LFT composite material by adopting the conventional method.

The detection results of the alkali-free glass fiber and LFT composite material for the prepared LFT reinforced polypropylene are shown in Table 1.

The odor detection is carried out according to the popular PV3900-2000 test standard.

TABLE 1 compositions of glass fiber impregnating compositions of examples 1 to 5 and comparative example 1 and results of product testing

The weight ratio of the effective components in table 1 is the total weight ratio of the coupling agent, the lubricant, the film forming agent a and the film forming agent B.

As can be seen from Table 1, the tensile strength, flexural strength and impact strength of examples 1 to 5 are similar to those of comparative example 1, but the odor test results show that examples 1 to 5 are significantly superior to comparative example 1.