CN101153091B - Additive for pultruded FRP products and preparation method thereof - Google Patents

Abstract

The present invention relates to an additive for pultruded glass steel products and a preparation method thereof. The additive for pultruded glass steel products is characterized in that the additive is prepared by high-carbon fatty alcohol, phosphorus pentoxide and organic amine used as raw materials. The molar ratio of the high-carbon fatty alcohol, phosphorus pentoxide and organic amine is (1.5 to 3.5) : 1.0 : (0.1 to 0.4). The preparation method of the additive for pultruded glass steel products is characterized in that the method comprises the following steps: the high-carbon fatty alcohol, phosphorus pentoxide and organic amine are weighed for preparation according to the molar ratio of the high-carbon fatty alcohol, phosphorus pentoxide and organic amine of (1.5 to 3.5) : 1.0 : (0.1 to 0.4). At first, the high-carbon fatty alcohol and phosphorus pentoxide do the esterification reaction; then the organic amine is added for neutralization reaction to prepare the additive for pultruded glass steel products. The additive for pultruded glass steel products of the present invention is colorless, transparent, close to neutrality, and has the functions of internal demoulding and fire resistance.

Description

Additive for pultruded FRP products and preparation method thereof

technical field

The invention relates to an additive used in pultruded FRP products and a preparation method thereof.

Background technique

The pultrusion molding process is a special process in the FRP molding process. The continuous fiber bundles (glass fibers, carbon fibers, etc.) and felts impregnated with resin glue are extruded and solidified through the mold under the action of traction. Continuously produce FRP products of unlimited length, with flexible design and easy molding.

During the molding process of the product, a strong adhesive force will be generated between the molded product and the surface of the metal mold. In order to prevent the additional load of the molded FRP product from sticking to the metal mold, a release must be applied between the product and the metal mold The agent is used so that the product can be easily released from the mold, so as to ensure the surface quality of the product and the integrity of the mold. In the early pultrusion molding process, external release agents were often used, and silicone oil was commonly used. In use, the release agent is put into a special tank. When the product is pulled, the release agent is brought to the surface of the resin-impregnated glass fiber molding, and then enters the mold to form and solidify to achieve the release effect. The release agent is used in a large amount and the surface quality of the product is not ideal, so the internal release agent has been used instead. In the FRP pultrusion process, the most used internal release agent is zinc stearate. However, due to the high viscosity of the resin, it is difficult to mix evenly when directly adding powdered zinc stearate, and the zinc stearate is loose, large in size, and entrained There is more air, resulting in more bubbles in the resin and poor surface gloss of the product. Therefore, in pultrusion production, people usually prefer to use an internal release agent that is liquid at room temperature, such as alkyl phosphate, which has many advantages: (1) It is easy to disperse in the resin; (2) , Improve production efficiency while reducing pultrusion resistance; (3), can reduce the surface tension of the resin mixture, reduce the viscosity of the resin, improve the wettability of the resin to the reinforcing material and filler, and improve the fluidity of the resin; (4), auxiliary Defoaming and improving the surface quality of parts, so that the surface of the product is smooth; (5), does not affect the curing characteristics of the resin, does not change the pot life of the mixed resin, does not affect the physical and mechanical properties of the product, does not affect the weather resistance of the product, etc. However, most of the currently commercially available alkyl phosphate internal release agents are acidic, so the following problems will occur in use: (1), when using acid-sensitive pigments, it will cause color changes; (2), in When using basic fillers, such as calcium carbonate, the acid release agent will react with it, causing the viscosity of the mixture to increase, but it will not affect the release effect; (3), if the filler is aluminum hydroxide, the acid release agent In addition to increasing the viscosity of the mixture, it will also release water during the curing process of the mixture, causing problems such as bubbles and cracks. In addition, most of the currently commercially available alkyl phosphate internal mold release agents are yellow, which limits their use in the production of colorless FRP products.

FRP products formed by the pultrusion process have the characteristics of light weight, high strength, good corrosion resistance, good electrical insulation performance, and high light transmittance. They are widely used in chemical anti-corrosion, construction, shipbuilding, vehicles, electrical engineering, light industry, and daily use. However, since the synthetic resins used in FRP are organic polymer compounds, such as unsaturated polyester resin, epoxy resin, phenolic resin, etc., which mainly contain carbon and hydrogen elements, they are extremely flammable. Therefore, it is important to improve the flame retardancy of FRP products. issues that urgently need to be resolved.

Halogen-free, low-smoke, low-toxic environment-friendly flame retardants have always been the goal pursued by people. Aluminum hydroxide, magnesium hydroxide, antimony trioxide, etc. are widely used in the production of FRP as cheap fillers and flame retardants. However, it needs to be added in a large amount, which affects the physical and mechanical properties of FRP products. Developed and widely used organophosphorus halogen-free phosphate flame retardants, such as triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, xylyl phosphate, xylene diphenyl phosphate etc., the flame retardant effect is not good, and its main function is plasticizing. New phosphorus-nitrogen synergistic flame retardants, such as melamine phosphate, are an important direction of current research. The outstanding advantages of phosphorus-nitrogen flame retardant systems are small additions, good flame retardant effect, and the released gas Low toxicity.

Contents of the invention

The object of the present invention is to provide a colorless, transparent, near-neutral, internal mold release and flame-retardant additive for pultruded FRP products and a preparation method thereof.

In order to achieve the above object, the technical solution of the present invention is: pultruded FRP product additive, which is characterized in that it is prepared from high-carbon fatty alcohol, phosphorus pentoxide and organic amine raw materials, high-carbon fatty alcohol, phosphorus pentoxide, The molar ratio of organic amine is 1.5-3.5:1.0:0.1-0.4.

The high-carbon fatty alcohol is a monohydric alcohol in the C6-C12 range or a mixture of monohydric alcohols in the C6-C12 range, such as any one of n-octanol, n-decyl alcohol, lauryl alcohol, etc. or any mixture of more than one , when any one or more are mixed, it is an arbitrary proportion.

The phosphorus pentoxide is analytically pure with a purity greater than 98wt%.

Described organic amine is aliphatic amines such as triethylamine, diethylamine or triethanolamine.

The preparation method of the above-mentioned pultruded FRP product additive is characterized in that it comprises the following steps:

1) Weigh the high-carbon fatty alcohol, phosphorus pentoxide, and organic amine according to the molar ratio of high-carbon fatty alcohol, phosphorus pentoxide, and organic amine of 1.5-3.5: 1.0: 0.1-0.4, and set aside;

2) In a four-necked flask equipped with a stirrer, a condenser, and a thermometer, add high-carbon aliphatic alcohol, put the four-necked flask into an ice-water bath, and pass nitrogen protection into the four-necked flask, and start stirring;

3) When the temperature of the four-necked flask is lower than 5°C, add phosphorus pentoxide to the four-necked flask, and stir vigorously, stop adding phosphorus pentoxide when the temperature is higher than 15°C; When the temperature is lower than 5°C, add phosphorus pentoxide again, and repeat this process until all phosphorus pentoxide is added (the time spent is 0.5-1.0 hours);

4) Remove the ice-water bath of the four-necked flask, and continue stirring to room temperature to obtain a turbid liquid in which phosphorus pentoxide is uniformly dispersed in high-carbon fatty alcohols, then put the four-necked flask into an oil bath, and heat up to 65-75°C for Esterification reaction, after 0.5 hours, it becomes a colorless and transparent liquid with a certain viscosity, and continues to react for 2.0-3.0 hours;

5) Remove the oil bath of the four-necked flask, stop heating and continue to stir to room temperature, then put the four-necked flask into an ice-water bath, and add liquid organic amine dropwise to the four-necked flask for neutralization reaction when the temperature is lower than 20°C , Additives for pultruded FRP products (it is a colorless and transparent near-neutral alkyl phosphate amine salt compound).

The present invention overcomes two major shortcomings of the currently commercially available alkyl phosphate release agent for pultruded FRP products: the one has a color (light yellow), and the other is that the acidity is too strong (the pH value is about 1-3 ); the additive for pultruded FRP products prepared by the present invention is a colorless, transparent, nearly neutral alkyl phosphate amine salt compound, and has the functions of an internal release agent and a flame retardant.

Compared with existing products, product of the present invention has the following advantages:

1) The product is colorless and transparent: it is a colorless and transparent liquid at room temperature with low viscosity and can be used in the production of colorless pultruded FRP products, expanding the scope of use.

2) The PH value of the product is high and close to neutral, which can protect the metal mold from corrosion and prolong the service life of the mold; at the same time, it hardly reacts with alkaline fillers, so it will not thicken the rubber compound and has good fluidity.

3) The product is used in pultruded FRP products. It not only has the function of internal release agent, but also is a phosphorus-nitrogen synergistic system flame retardant, which has the function of flame retardant.

Detailed ways

In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the content of the present invention is not limited to the following examples.

Example 1:

Additive for pultruded FRP products. It is prepared from high-carbon fatty alcohol (ROH), phosphorus pentoxide (P ₂ O ₅ ) and organic amine raw materials. The molar ratio of high-carbon fatty alcohol, phosphorus pentoxide and organic amine is 2.5:1.0:0.3. The high-carbon aliphatic alcohol is n-octanol; the phosphorus pentoxide is analytically pure, with a purity greater than 98% by weight; the organic amine is triethylamine.

The preparation method of the above-mentioned pultruded glass fiber reinforced plastic product additive, it comprises the steps:

1) Take high-carbon fatty alcohol, phosphorus pentoxide, organic amine according to the molar ratio of high-carbon fatty alcohol, phosphorus pentoxide, organic amine is 2.5: 1.0: 0.3, standby; Described high-carbon fatty alcohol is positive Octanol; Described organic amine is triethylamine;

2) In a four-necked flask equipped with a stirrer, a condenser, and a thermometer, add high-carbon aliphatic alcohol, put the four-necked flask into an ice-water bath, and pass nitrogen protection into the four-necked flask, and start stirring;

3) When the temperature of the four-necked flask is lower than 5°C, add phosphorus pentoxide to the four-necked flask, and stir vigorously, stop adding phosphorus pentoxide when the temperature is higher than 15°C; When the temperature is lower than 5°C, add phosphorus pentoxide again, and repeat this process until all phosphorus pentoxide is added (the time spent is 0.5-1.0 hours);

4) Remove the ice-water bath of the four-necked flask, and continue stirring to room temperature to obtain a cloudy liquid in which phosphorus pentoxide is uniformly dispersed in high-carbon fatty alcohols, then put the four-necked flask into an oil bath, and heat up to 70°C for esterification After 0.5 hours of reaction, it becomes a colorless and transparent liquid with a certain viscosity, and continues to react for 2.0-3.0 hours;

5) Remove the oil bath of the four-necked flask, stop heating and continue to stir to room temperature, then put the four-necked flask into an ice-water bath, and add liquid organic amine dropwise to the four-necked flask for neutralization reaction when the temperature is lower than 20°C , the neutralization reaction time is 2.0-3.0 hours, and the additive for pultruded FRP products (it is a colorless and transparent near-neutral alkyl phosphate amine salt compound) is obtained.

The test results of the basic physical properties of the additives for pultruded FRP products are shown in Table 1.

Example 2:

The preparation method is the same as in Example 1, and n-octanol is replaced with a monohydric alcohol mixture containing C8-C12 range (such as the mixture of n-decyl alcohol and lauryl alcohol, and the moles of n-decyl alcohol and lauryl alcohol each account for 1/3 of the high-carbon aliphatic alcohol. 2). The test results of the basic physical properties of the additives for pultruded FRP products are shown in Table 1.

Example 3:

The preparation method is the same as in Example 1, except that triethylamine is replaced by triethanolamine. The test results of the basic physical properties of the additives for pultruded FRP products are shown in Table 1.

Example 4:

The preparation method is the same as in Example 3, and n-octanol is replaced with a monohydric alcohol mixture containing C8-C12 range (such as the mixture of n-decyl alcohol and lauryl alcohol, and the moles of n-decyl alcohol and lauryl alcohol each account for 1/3 of the high-carbon aliphatic alcohol. 2). The test results of the basic physical properties of the additives for pultruded FRP products are shown in Table 1.

Table 1, Basic physical performance test results

Application in pultruded FRP products:

Application example 1:

The glue formulation of the pultruded FRP profile is: 100 parts (weight) of general-purpose unsaturated polyester resin, 2 parts (weight) of methyl ethyl ketone peroxide, 3 parts (weight) of cobalt naphthalate solution, 20 parts (weight) of calcium carbonate, 2 parts (weight) of the pultruded FRP product additive (alkyl phosphate amine salt compound) prepared in Example 1; the reinforcing material adopts glass fiber roving: 2600Tex (grams per kilometer), in the pultruded FRP profile The weight fraction is 75%; the pultrusion speed is 30-40cm/min; the temperature setting of the mold three zones: 100°C in zone I, 120°C in zone II, and 130°C in zone III. The test results of the basic physical properties of the profiles are shown in Table 2.

Application example 2:

The preparation method is the same as that of Application Example 1, except that the pultruded FRP product additive (alkyl phosphate amine salt compound) prepared in Example 1 is not added. The test results of the basic physical properties of the profiles are shown in Table 2.

Application example 3:

The preparation method is the same as that of Application Example 1, except that the pultruded FRP product additive (alkyl phosphate amine salt compound) prepared in Example 1 is replaced with zinc stearate. The test results of the basic physical properties of the profiles are shown in Table 2.

Table 2. Test results of basic physical properties of pultruded FRP profiles

Example 5:

The additive for pultruded FRP products is prepared from high-carbon fatty alcohol, phosphorus pentoxide and organic amine raw materials, and the molar ratio of high-carbon fatty alcohol, phosphorus pentoxide and organic amine is 1.5:1.0:0.1.

The high-carbon aliphatic alcohol is n-decyl alcohol; the phosphorus pentoxide is analytically pure with a purity greater than 98% by weight; the organic amine is diethylamine.

The preparation method of the above-mentioned pultruded glass fiber reinforced plastic product additive, it comprises the steps:

1) Take high-carbon fatty alcohol, phosphorus pentoxide, organic amine according to the molar ratio of high-carbon fatty alcohol, phosphorus pentoxide, organic amine is 1.5: 1.0: 0.1, standby; Described high-carbon fatty alcohol is positive Decyl alcohol; the described phosphorus pentoxide is analytically pure, with a purity greater than 98wt%; the described organic amine is diethylamine;

2) In a four-necked flask equipped with a stirrer, a condenser, and a thermometer, add high-carbon aliphatic alcohol, put the four-necked flask into an ice-water bath, and pass nitrogen protection into the four-necked flask, and start stirring;

3) When the temperature of the four-necked flask is lower than 5°C, add phosphorus pentoxide to the four-necked flask, and stir vigorously, stop adding phosphorus pentoxide when the temperature is higher than 15°C; When the temperature is lower than 5°C, add phosphorus pentoxide again, and repeat this process until all phosphorus pentoxide is added (the time spent is 0.5-1.0 hours);

4) Remove the ice-water bath of the four-necked flask, and continue stirring to room temperature to obtain a cloudy liquid in which phosphorus pentoxide is uniformly dispersed in high-carbon fatty alcohols, then put the four-necked flask into an oil bath, and heat up to 65°C for esterification After 0.5 hours of reaction, it becomes a colorless and transparent liquid with a certain viscosity, and continues to react for 2.0-3.0 hours;

5) Remove the oil bath of the four-necked flask, stop heating and continue to stir to room temperature, then put the four-necked flask into an ice-water bath, and add liquid organic amine dropwise to the four-necked flask for neutralization reaction when the temperature is lower than 20°C , the neutralization reaction time is 2.0-3.0 hours, and the additive for pultruded FRP products (it is a colorless and transparent near-neutral alkyl phosphate amine salt compound) is obtained.

Embodiment 6:

The additive for pultruded FRP products is prepared from high-carbon fatty alcohol, phosphorus pentoxide and organic amine raw materials. The molar ratio of high-carbon fatty alcohol, phosphorus pentoxide and organic amine is 3.5:1.0:0.4.

The high-carbon fatty alcohol is a mixture of n-octanol, n-decyl alcohol and lauryl alcohol, and the moles of n-octanol, n-decyl alcohol and lauryl alcohol respectively account for 1/3 of the high-carbon fatty alcohol; Phosphorus is analytically pure with a purity greater than 98wt%; the organic amine is triethanolamine;

The preparation method of the above-mentioned pultruded glass fiber reinforced plastic product additive, it comprises the steps:

1) Weigh the high-carbon fatty alcohol, phosphorus pentoxide, and organic amine according to the molar ratio of high-carbon fatty alcohol, phosphorus pentoxide, and organic amine of 1.5-3.5: 1.0: 0.1-0.4, and set aside; Fatty alcohol is the mixture of n-octyl alcohol, n-decyl alcohol and lauryl alcohol, and the moles of n-octyl alcohol, n-decyl alcohol and lauryl alcohol respectively account for 1/3 of high-carbon fatty alcohol; described phosphorus pentoxide is analytically pure, The purity is greater than 98wt%; the organic amine is triethanolamine;

2) In a four-necked flask equipped with a stirrer, a condenser, and a thermometer, add high-carbon aliphatic alcohol, put the four-necked flask into an ice-water bath, and pass nitrogen protection into the four-necked flask, and start stirring;

3) When the temperature of the four-necked flask is lower than 5°C, add phosphorus pentoxide to the four-necked flask, and stir vigorously, stop adding phosphorus pentoxide when the temperature is higher than 15°C; When the temperature is lower than 5°C, add phosphorus pentoxide again, and repeat this process until all phosphorus pentoxide is added (the time spent is 0.5-1.0 hours);

4) Remove the ice-water bath of the four-necked flask, and continue to stir to room temperature to obtain a cloudy liquid in which phosphorus pentoxide is uniformly dispersed in high-carbon fatty alcohols, then put the four-necked flask into an oil bath, and heat up to 75°C for esterification After 0.5 hours of reaction, it becomes a colorless and transparent liquid with a certain viscosity, and continues to react for 2.0-3.0 hours;

5) Remove the oil bath of the four-necked flask, stop heating and continue to stir to room temperature, then put the four-necked flask into an ice-water bath, and add liquid organic amine dropwise to the four-necked flask for neutralization reaction when the temperature is lower than 20°C , the neutralization reaction time is 2.0-3.0 hours, and the additive for pultruded FRP products (it is a colorless and transparent near-neutral alkyl phosphate amine salt compound) is obtained.

Claims (4)

1. additive agent for dragging and squeezing glass fiber reinforced plastics product is characterized in that it is formed by high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES and organic amine feedstock production, and the mol ratio of high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine is 1.5-3.5: 1.0: 0.1-0.4;

Described high-carbon fatty alcohol is the mixture of the monohydroxy-alcohol of the monohydroxy-alcohol of C6-C12 scope or C6-C12 scope; Described organic amine is triethylamine, diethylamine or trolamine.

2. additive agent for dragging and squeezing glass fiber reinforced plastics product according to claim 1 is characterized in that: the monohydroxy-alcohol of C6-C12 scope is n-Octanol, nonylcarbinol or lauryl alcohol.

3. additive agent for dragging and squeezing glass fiber reinforced plastics product according to claim 1 is characterized in that: described Vanadium Pentoxide in FLAKES is an analytical pure, and purity is greater than 98wt%.

4. the preparation method of additive agent for dragging and squeezing glass fiber reinforced plastics product as claimed in claim 1 is characterized in that it comprises the steps:

1) mol ratio by high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine is 1.5-3.5: 1.0: 0.1-0.4 takes by weighing high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine, and is standby;

Described high-carbon fatty alcohol is the mixture of the monohydroxy-alcohol of the monohydroxy-alcohol of C6-C12 scope or C6-C12 scope; Described organic amine is triethylamine, diethylamine or trolamine;

2) in the four-hole boiling flask that agitator, prolong, thermometer are housed, add high-carbon fatty alcohol, four-hole boiling flask is put into ice-water bath, and logical nitrogen protection in four-hole boiling flask, starts stirring;

3) when the temperature of four-hole boiling flask is lower than 5 ℃, in four-hole boiling flask, add Vanadium Pentoxide in FLAKES, and powerful the stirring, when being higher than 15 ℃, temperature stops to add Vanadium Pentoxide in FLAKES; When the temperature of four-hole boiling flask is lower than 5 ℃ once more, add Vanadium Pentoxide in FLAKES again, as follows repeatedly, till adding all Vanadium Pentoxide in FLAKESs;

4) remove the ice-water bath of four-hole boiling flask, continue to be stirred to room temperature, obtain Vanadium Pentoxide in FLAKES homodisperse turbid liquid in high-carbon fatty alcohol, then four-hole boiling flask is put into oil bath, be warming up to 65-75 ℃ and carry out esterification, the transparent liquid that certain viscosity is arranged 0.5 promptly become colorless after hour continues reaction 2.0-3.0 hour;

5) remove the oil bath of four-hole boiling flask, stop heating and continue to be stirred to room temperature, then four-hole boiling flask is put into ice-water bath, be lower than 20 ℃, in four-hole boiling flask, drip the liquid organic amine and carry out neutralization reaction in temperature, must additive agent for dragging and squeezing glass fiber reinforced plastics product.