阅读说明：本技术 一种新型玻璃纤维用成膜剂的制备方法 (Preparation method of novel film-forming agent for glass fiber ) 是由 宣维栋 赵建新 柴雪虹 金湘玉 安宝民 于 2019-11-18 设计创作，主要内容包括：一种新型玻璃纤维用成膜剂的制备方法,本发明涉及成膜剂技术领域,将30%～70%的双酚A型环氧树脂加热至70～80℃；在路易斯酸催化下,使双酚A型环氧树脂与聚氧化乙烯进行接枝反应制得双酚A型环氧树脂-聚氧化乙烯接枝共聚物；将0.1%～10%的环氧乙烷-环氧丙烷嵌段共聚物、6%～10%的双酚A型环氧树脂-聚氧化乙烯接枝共聚物以及上述加热后的双酚A型环氧树脂按照配比加入到乳化釜内,在60～70℃的温度下搅拌均匀；打开搅拌电机,在1000～1500转/分钟的搅拌速度下缓慢加入去离子水,至物料转变为水性后,继续加水稀释至乳液固含量为50±1.0%,即得粒径为0.47-0.72微米的成膜剂。(The invention discloses a preparation method of a novel film-forming agent for glass fibers, which relates to the technical field of film-forming agents, and is characterized in that 30-70% of bisphenol A epoxy resin is heated to 70-80 ℃; under the catalysis of Lewis acid, bisphenol A epoxy resin and polyoxyethylene are subjected to grafting reaction to prepare a bisphenol A epoxy resin-polyoxyethylene graft copolymer; adding 0.1-10% of ethylene oxide-propylene oxide block copolymer, 6-10% of bisphenol A type epoxy resin-polyethylene oxide graft copolymer and the heated bisphenol A type epoxy resin into an emulsifying kettle according to the proportion, and uniformly stirring at the temperature of 60-70 ℃; and (3) starting a stirring motor, slowly adding deionized water at a stirring speed of 1000-1500 rpm until the materials are changed into water, and continuously adding water to dilute until the solid content of the emulsion is 50 +/-1.0%, so as to obtain the film-forming agent with the particle size of 0.47-0.72 microns.)

1. A preparation method of a novel film forming agent for glass fiber is characterized by comprising the following steps: the preparation method comprises the following steps:

(1) heating 30-70% of bisphenol A epoxy resin to 70-80 ℃;

(2) under the catalysis of Lewis acid, bisphenol A epoxy resin and polyoxyethylene are subjected to grafting reaction to prepare bisphenol A epoxy resin-polyoxyethylene graft copolymer;

(3) adding 0.1-10% of ethylene oxide-propylene oxide block copolymer, 6-10% of bisphenol A type epoxy resin-polyethylene oxide graft copolymer and the heated bisphenol A type epoxy resin into an emulsifying kettle according to the proportion, and uniformly stirring at the temperature of 60-70 ℃;

(4) and turning on a stirring motor, slowly adding deionized water at a stirring speed of 1000-1500 rpm until the materials are changed into water, and continuously adding water to dilute until the solid content of the emulsion is 50 +/-1.0%, thus obtaining the film-forming agent with the particle size of 0.47-0.72 microns.

2. The method for preparing a novel film-forming agent for glass fiber according to claim 1, wherein: the bisphenol A epoxy resin has an epoxy equivalent of 185-206.

3. The method for preparing a novel film-forming agent for glass fiber according to claim 1, wherein: the molecular weight of the polyoxyethylene is 100000-1000000.

4. The method for preparing a novel film-forming agent for glass fiber according to claim 1, wherein: the Lewis acid is aluminum chloride, ferric chloride, boron trifluoride or trifluoromethanesulfonate.

5. The method for preparing a novel film-forming agent for glass fiber according to claim 1, wherein: its application is as follows: mixing the film forming agent with a silane coupling agent, a non-ionic lubricant and a softening agent to prepare a sizing agent, wherein the usage amount of the film forming agent is 5-8 wt%, namely the film forming agent occupies more than 65% of effective components; the film forming agent is applied to a drawing process of glass fiber yarns, and is used for enhancing the shearing strength of the yarns, reducing the variability and simultaneously reducing the fiber content; the film forming agent is applied to glass fiber products, is used for improving the linear density, the strength and the soaking speed of the glass fiber products, and is also used for reducing the water content and the combustible content of the glass fiber products; the film forming agent is applied to the preparation of the glass fiber reinforced plastic gas cylinder and is used for reducing the damage degree of the glass fiber reinforced plastic gas cylinder, so that the cracking condition of the glass fiber reinforced plastic gas cylinder is improved.

Technical Field

The invention relates to the technical field of film forming agents, in particular to a preparation method of a novel film forming agent for glass fibers.

Background

CNG, Compressed Natural Gas (CNG), is Natural Gas that is pressurized and stored in a gaseous state in a container. The compressed natural gas can be used for producing biogas (the main component is methane) artificially besides natural gas in oil fields and natural gas fields. The composition of the compressed natural gas is the same as that of the pipeline natural gas, and the main component of the compressed natural gas is methane (CH 4). CNG can be used as a vehicle fuel. CNG may be used to make LNG (Liquefied Natural Gas). CNG fueled vehicles are called ngv (naturalgasgashvel). Liquefied Petroleum Gas (LPG) is often confused with LNG, and indeed they are clearly distinguished. The main component of LPG is propane (over 95%) with small amounts of butane, which is stored in liquid form under appropriate pressure in tank containers and is used as domestic and vehicle fuel. Compared with gasoline, the compressed natural gas has the advantages of higher safety, better fuel anti-explosion performance, fuel cost saving, transportation cost reduction, maintenance period extension, environmental protection and the like.

With the development of gas vehicle technology and the development of glass fiber reinforced plastic technology, the performance of the natural gas cylinder for the vehicle is greatly improved when the natural gas cylinder for the vehicle is transited from a steel cylinder to a glass fiber reinforced plastic cylinder. Compared with the traditional steel cylinder, the glass fiber reinforced plastic gas cylinder has the advantages of high specific strength, good shock absorption, good damage safety and the like.

Disclosure of Invention

The invention aims to provide a preparation method of a novel film-forming agent for glass fiber, which is reasonable in design and aims at overcoming the defects and shortcomings of the prior art, the novel film-forming agent for glass fiber is prepared by adopting 6-10% of bisphenol A epoxy resin-polyethylene oxide graft copolymer, wherein a polyether chain segment is arranged in the middle of the copolymer, and epoxy groups are arranged at two ends of the copolymer, so that the copolymer has better compatibility with bisphenol A epoxy resin, and when the copolymer is used as a film-forming agent for glass fiber, the epoxy groups at two ends can participate in curing reaction in the subsequent process, so that the mechanical property of the material is improved.

In order to achieve the purpose, the preparation method of the novel film forming agent for the glass fiber, disclosed by the invention, comprises the following preparation steps:

1. heating 30-70% of bisphenol A epoxy resin to 70-80 ℃;

2. under the catalysis of Lewis acid, bisphenol A epoxy resin and polyoxyethylene are subjected to grafting reaction to prepare a bisphenol A epoxy resin-polyoxyethylene graft copolymer;

3. adding 0.1-10% of ethylene oxide-propylene oxide block copolymer, 6-10% of bisphenol A type epoxy resin-polyethylene oxide graft copolymer and the heated bisphenol A type epoxy resin into an emulsifying kettle according to the proportion, and uniformly stirring at the temperature of 60-70 ℃;

4. and (3) starting a stirring motor, slowly adding deionized water at a stirring speed of 1000-1500 rpm until the materials are changed into water, and continuously adding water to dilute until the solid content of the emulsion is 50 +/-1.0%, so as to obtain the film-forming agent with the particle size of 0.47-0.72 microns.

Further, the bisphenol A type epoxy resin has an epoxy equivalent of 185-206.

Further, the molecular weight of the polyoxyethylene is 100000-1000000.

Further, the Lewis acid is aluminum chloride, ferric chloride, boron trifluoride or trifluoromethanesulfonate.

The preparation method of the novel film-forming agent for glass fiber disclosed by the invention is applied as follows:

mixing the film forming agent with a silane coupling agent, a non-ionic lubricant and a softening agent to prepare a sizing agent, wherein the usage amount of the film forming agent is 5-8 wt%, namely the film forming agent occupies more than 65% of effective components; the film forming agent is applied to a drawing process of glass fiber yarns, and is used for enhancing the shearing strength of the yarns, reducing the variability and simultaneously reducing the fiber content; the film forming agent is applied to glass fiber products, is used for improving the linear density, the strength and the soaking speed of the glass fiber products, and is also used for reducing the water content and the combustible content of the glass fiber products; the film forming agent is applied to the preparation of the glass fiber reinforced plastic gas cylinder and is used for reducing the damage degree of the glass fiber reinforced plastic gas cylinder, so that the cracking condition of the glass fiber reinforced plastic gas cylinder is improved.

When the dosage of the bisphenol A type epoxy resin-polyoxyethylene graft copolymer is lower than 6 percent, the prepared film-forming agent has larger particles, the prepared glass fiber has slower soaking speed and poorer mechanical property, so that a qualified gas cylinder for a vehicle can not be manufactured; when the dosage is higher than 10%, the production cost is increased, and the related performance of the glass fiber is also influenced, so that the invention selects 6-10% of bisphenol A type epoxy resin-polyoxyethylene graft copolymer, which not only can reduce the utilization of the film forming agent, but also can improve the permeation speed of the glass fiber prepared by using the film forming agent, improve the mechanical property of the glass fiber, and also can reduce the production cost.

The invention has the beneficial effects that: the invention provides a preparation method of a novel film-forming agent for glass fiber with reasonable design, which adopts 6-10% of bisphenol A type epoxy resin-polyoxyethylene graft copolymer, wherein the middle part of the copolymer is a polyether chain segment, and the two ends of the copolymer are epoxy groups, so that the copolymer not only has better compatibility with bisphenol A type epoxy resin, but also can participate in curing reaction when being used as a film-forming agent applied to glass fiber in the subsequent working procedure processing process, thereby improving the mechanical property of the material.

Description of the drawings:

FIG. 1 is a table of the performance tests of the hansen film former used in the drawing process of glass fiber yarns in the first embodiment and in the prior art.

FIG. 2 is a table of the performance of the first example of a Hansen film former in a fiberglass article.

FIG. 3 is a table of performance tests of the first example with a Hansen film former in the preparation of a fiberglass cylinder.

The specific implementation mode is as follows:

the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The preparation method of the novel film-forming agent for glass fiber described in the present embodiment (example one) comprises the following steps:

1. heating 53% bisphenol A type epoxy resin (trade name E51, epoxy equivalent of 196) to 75 ℃;

2. under the catalysis of Lewis acid (aluminum chloride), bisphenol A epoxy resin and polyoxyethylene (with the molecular weight of 500000-550000) are subjected to a grafting reaction to prepare a bisphenol A epoxy resin-polyoxyethylene graft copolymer;

3. adding 3% of ethylene oxide-propylene oxide block copolymer, 7% of bisphenol A epoxy resin-polyethylene oxide graft copolymer and the heated bisphenol A epoxy resin into an emulsifying kettle according to the proportion, and uniformly stirring at the temperature of 65 ℃;

4. turning on a stirring motor, slowly adding deionized water at a stirring speed of 1200 rpm until the materials are changed into water, and continuously adding water to dilute until the solid content of the emulsion is 50%, so as to obtain the film-forming agent with the particle size of 0.47 microns, wherein the dilution stability is as follows: 5% upper layer 4.94, 5% lower layer 5.13, difference 0.19; the centrifugal stability was as follows: the upper layer is 0.5mL of clear water.

The beneficial effects of the embodiment are as follows: the specific embodiment provides a preparation method of a novel film-forming agent for glass fiber with reasonable design, which adopts 6-10% of bisphenol A epoxy resin-polyoxyethylene graft copolymer, the middle of the copolymer is a polyether chain segment, and the two ends of the copolymer are epoxy groups, so that the copolymer not only has better intermiscibility with bisphenol A epoxy resin, but also can participate in curing reaction when being applied to the glass fiber as the film-forming agent in the processing process of the back procedure, thereby improving the mechanical property of the material.