TW202035664A - Halogen-free flame-retardant composition and halogen-free flame-retardant fiber reinforced plastic plate including halogen-free flame-retardant unsaturated polyester, filler and fiber - Google Patents

Abstract

Disclosed is a halogen-free flame-retardant composition, which comprises a halogen-free flame-retardant unsaturated polyester, a filler and fibers. The halogen-free flame-retardant unsaturated polyester is formed by reacting with reacted components as shown in formula (I) which comprises a phosphorus-containing flame-retardant monomer, an alcohol component and an acid component, wherein the acid component comprises at least one of polyacid and polyanhydride, and weighted according to the sum (100wt%) of weights of the phosphorus-containing flame-retardant monomer, the alcohol component and the acid component as shown in the formula (I), the weight of the phosphorus-containing flame-retardant monomer as shown in the formula (I) is greater than 0.75wt% and lower than 7.5w%. Weighted according to the total weight (100wt%) of a halogen-free flame-retardant fiber reinforced plastic plate, the weight of the halogen-free flame-retardant unsaturated polyester is 10wt% to 38wt%, and the weight of the filler is greater than 12wt% and lower than 40wt%.

Description

Halogen-free flame-resistant composition and halogen-free flame-resistant fiber reinforced plastic board

The present invention relates to a flame-resistant composition and a fiber-reinforced plastic board, in particular to a halogen-free flame-resistant composition and a halogen-free flame-resistant fiber-reinforced plastic board.

Mainland China Patent Publication No. 103160097 discloses a flame-retardant unsaturated polyester glass fiber reinforced plastic molding compound, which contains unsaturated polyester resin, low shrinkage additives, initiators, polymerization inhibitors, thickeners, fillers, mold release agents, and reinforcement Fiber, wherein the unsaturated polyester resin is a brominated bisphenol A type unsaturated polyester resin.

Although the patent case uses brominated bisphenol A unsaturated polyester resin, the unsaturated polyester FRP molding compound has flame retardancy. However, the unsaturated polyester FRP molding compound releases halogen-containing toxic fumes at high temperatures, which makes the use of materials for public transportation and construction very limited.

Therefore, one object of the present invention is to provide a halogen-free flame-resistant composition with low smoke toxicity and high oxygen index.

式(I) R表示含有二羥基(-OH)的基團或含有二羧酸(-COOH)基的基團。Therefore, the halogen-free flame-retardant composition of the present invention includes a halogen-free flame-retardant unsaturated polyester, a filler, and fibers. The halogen-free flame-retardant unsaturated polyester is formed by reacting a reaction composition comprising a phosphorus-containing flame-retardant monomer represented by formula (I), an alcohol component and an acid component, wherein the acid component includes a multi-component At least one of an acid and a polybasic acid anhydride, and the sum of the amounts of the phosphorus-containing flame-retardant monomer represented by the formula (I), the alcohol component and the acid component is 100% by weight, the formula (I) The amount of phosphorus-containing flame-retardant monomers is greater than 0.75wt% and 7.5wt% or less. Based on the total amount of the halogen-free flame-retardant fiber-reinforced plastic board as 100wt%, the amount of the halogen-free flame-retardant unsaturated polyester is 10wt% to 38wt%, and the amount of filler is greater than 12wt% and less than 40wt%,

Formula (I) R represents a group containing a dihydroxy (-OH) group or a group containing a dicarboxylic acid (-COOH) group.

Another object of the present invention is to provide a halogen-free flame-resistant fiber reinforced plastic panel.

The halogen-free flame-resistant fiber-reinforced plastic board of the present invention is formed from the above-mentioned halogen-free flame-resistant composition.

The effect of the present invention is that by using the phosphorus-containing flame-retardant monomer shown in formula (I) and matching the amount of each component, the halogen-free flame-resistant composition can make halogen-free flame-resistant fiber reinforced plastic panels have high oxygen index and low Smoke toxicity.

式(I) R表示含有二羥基(-OH)的基團或含有二羧酸(-COOH)基的基團。The halogen-free flame-retardant composition of the present invention includes halogen-free flame-retardant unsaturated polyester, filler, and fiber. The halogen-free flame-retardant unsaturated polyester is formed by reacting a reaction composition comprising a phosphorus-containing flame-retardant monomer represented by formula (I), an alcohol component and an acid component, wherein the acid component includes a multi-component At least one of an acid and a polybasic acid anhydride, and the sum of the amounts of the phosphorus-containing flame-retardant monomer represented by the formula (I), the alcohol component and the acid component is 100% by weight, the formula (I) The amount of phosphorus-containing flame-retardant monomers is greater than 0.75wt% and 7.5wt% or less. Based on the total amount of the halogen-free flame-retardant fiber-reinforced plastic board as 100wt%, the amount of the halogen-free flame-retardant unsaturated polyester is 10wt% to 38wt%, and the amount of filler is greater than 12wt% and less than 40wt%,

Formula (I) R represents a group containing a dihydroxy (-OH) group or a group containing a dicarboxylic acid (-COOH) group.

[Halogen-free flame-retardant unsaturated polyester]

<Phosphorus-containing flame-retardant monomer represented by formula (I)>

，其中，R¹ 、R² 及R³ 表示烷基。在本發明的一些實施例中，該含有二羥基的基團為

。The dihydroxy-containing group such as

, Wherein R ¹ , R ² and R ³ represent an alkyl group. In some embodiments of the present invention, the dihydroxy-containing group is

.

，其中，R⁴ 表示烷基。在本發明的一些實施例中，該含有二羧酸基的基團為

。The group containing dicarboxylic acid groups such as

, Where R ⁴ represents an alkyl group. In some embodiments of the present invention, the group containing a dicarboxylic acid group is

.

In some embodiments of the present invention, based on the sum of the amounts of the phosphorus-containing flame-retardant monomer represented by the formula (I), the alcohol component and the acid component as 100% by weight, the formula (I) The amount of phosphorus-containing flame-retardant monomer is 3.75 wt% to 7.5 wt%.

<Alcohol component>

The alcohol component includes organic polyols. The organic polyol can be used singly or as a mixture of multiple types, and the organic polyols include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, dimethyl glycol, and diethylene glycol. Alcohol, butanediol, pentanediol, glycerol, oxyalkyl bisphenol, or hydrogenated bisphenol, etc.

＜Acid component＞

The polybasic acid can be used singly or in combination of multiple types, and the polybasic acid is, for example, an unsaturated polybasic acid. The unsaturated polybasic acid can be used singly or in combination of multiple types, and the unsaturated polybasic acid is for example but not limited to phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, soybean oil fatty acid, linseed oil Acid, itaconic acid, aconic acid, mesaconic acid, fumaric acid, isophthalic acid, or terephthalic acid, etc.

The polybasic acid anhydride can be used singly or in combination of multiple types, and the polybasic acid anhydride is for example an unsaturated polybasic acid anhydride. The unsaturated polybasic acid anhydride can be used singly or in combination of multiple types, and the unsaturated polybasic acid anhydride is for example, but not limited to, maleic anhydride or phthalic anhydride.

The reaction composition also includes a diluting monomer to adjust the viscosity of the halogen-free flame-retardant unsaturated polyester to facilitate easy operation in the process of mixing it with fillers and fibers. In addition, it can also be used as a crosslinking agent.

＜Diluted monomer＞

The diluting monomer includes at least one of a styrene-based monomer and an acrylate-based monomer.

The styrenic monomer can be used alone or in combination of multiple types, and the styrenic monomers include, but are not limited to, styrene, α-methylstyrene, ethyl vinyl benzene, vinyl benzoic acid, and vinyl toluene. , P-methylstyrene, p-chlorostyrene, or chloromethylstyrene, etc.

The acrylate-based monomers can be used alone or in combination of multiple types, and the acrylate-based monomers include, but are not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate Ester, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl methacrylate, stearyl methacrylate, ethylene two Alcohol acrylate, ethylene glycol (meth)acrylate, glycidyl acrylate, glycidyl methacrylate, tripropylene glycol diacrylate, or tripropylene glycol dimethacrylate, etc.

The reaction composition also includes an inhibitor.

<Inhibitor>

The inhibitor is for example but not limited to hydroquinone.

The preparation method of the halogen-free flame-retardant unsaturated polyester of the present invention can be carried out by any conventional polyester method, and is not particularly limited. For example, the acid component, the alcohol component and the phosphorus-containing flame-retardant monomer represented by formula (I) are subjected to condensation polymerization in an inert environment (such as a nitrogen environment) until the acid value is 10 mgKOH/g To 40 mgKOH/g, and then selectively add the diluting monomer and/or inhibitor to obtain the halogen-free flame-retardant unsaturated polyester.

[Filling Material]

The filler is, for example, an organic filler or an inorganic filler. The filler can be used alone or in a mixture of multiple, and the filler such as but not limited to aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, silicon dioxide, calcium carbonate, titanium dioxide, graphite, magnesium carbonate, molybdenum trioxide, Zinc borate, or zinc stannate, etc.

[fiber]

The fiber can be used alone or in a mixture of multiple types, and the fiber is for example, but not limited to, glass fiber, carbon fiber, silicon carbide fiber, boron fiber, aramid fiber, or ceramic fiber. In some embodiments of the present invention, based on the total amount of the halogen-free flame-resistant fiber-reinforced plastic board being 100% by weight, the amount of the fiber is 15% to 70% by weight.

The halogen-free flame retardant composition also contains a hardener.

[hardener]

The hardener can be used alone or in combination of multiple types, and the hardener is for example, but not limited to, ketone peroxide.

[Halogen-free flame-resistant fiber reinforced plastic panels]

The halogen-free flame-resistant fiber-reinforced plastic board of the present invention is formed from the above-mentioned halogen-free flame-resistant composition.

The preparation method of the halogen-free flame-resistant fiber-reinforced plastic panel of the present invention can be carried out by any conventional processing method, and there is no special limitation. The processing method is, for example, hand-laminated manufacturing method, spraying manufacturing method, vacuum bag manufacturing method, pultrusion manufacturing method, transfer molding manufacturing method, compression molding manufacturing method, continuous laminated manufacturing method, winding molding manufacturing method, or hot press molding manufacturing Law etc.

For example, the preparation method of the halogen-free flame-retardant fiber-reinforced plastic panel of the present invention includes: step (a), mixing halogen-free flame-retardant unsaturated polyester, filler, and hardener to form a mixture; step (b): The fibers are shaped to form a fiberboard; in step (c), the mixture is contacted with the fiberboard and undergoes a curing reaction to obtain a halogen-free flame-resistant fiber-reinforced plastic panel. It is worth noting that the preparation method of the halogen-free flame-retardant fiber-reinforced plastic panel of the present invention is not limited to the above examples.

The halogen-free flame-resistant fiber-reinforced plastic panel of the present invention is environmentally friendly because it is halogen-free, and also has high flame retardancy, low smoke toxicity, and excellent mechanical strength. In terms of flame retardancy, the halogen-free flame-resistant fiber-reinforced plastic panel of the present invention can pass the British BS6853 rail vehicle material fire test standard certification. The halogen-free flame-resistant fiber-reinforced plastic panel of the present invention can be used in fields such as rail vehicles, construction, automobile components, and marine applications. In the field of rail vehicles, the halogen-free flame-resistant fiber reinforced plastic panel of the present invention can pass the smoke toxicity test of ASTM E662 in the American NFPA130 rail vehicle material fire test standard certification.

The present invention will be further described with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limiting the implementation of the present invention.

Preparation Example 1 Halogen-free flame-retardant unsaturated polyester

The weight ratio of maleic anhydride, phthalic anhydride, [(6-oxo-6H-dibenzo[C,E][1,2]oxaphosphine with a weight ratio of 1:1:0.156:1:1:1 Hexylcyclo-6-yl)methyl]succinate bis(2-hydroxyethyl){Bis(2-hydroxyethyl)(6H-dibenz[c,e][1,2]oxaphosphorin-6-ylmethyl)succinate P-oxide, CAS registration number 63562-34-5}, a mixture of diethylene glycol and ethylene glycol, and a mixture with a total weight of 800 grams. The mixture was subjected to a condensation polymerization reaction at a temperature of 170°C to 230°C in a nitrogen environment, and mechanically stirred at a rotation speed of 150rpm. At the same time, the moisture generated during the reaction was removed, and the outlet of the moisture was removed. The temperature is controlled at 80°C to 120°C. When the acid value is lower than 40mgKOH/g, start to cool down to 80℃, and add 490 grams of styrene and 1 gram of hydroquinone to obtain 1227 grams of light yellow transparent substance with a viscosity of 300 cps, which is halogen-free Flame retardant unsaturated polyester.

Preparation Example 2 Halogen-free flame-retardant unsaturated polyester

The weight ratio is 1:1:0.031:1.05:1.05 maleic anhydride, phthalic anhydride, [(6-oxo-6H-dibenzo[C,E][1,2]oxaphosphine Hexylcyclo-6-yl)methyl] bis(2-hydroxyethyl) succinate, diethylene glycol, and ethylene glycol are mixed to form a mixture with a total weight of 800 grams. The mixture was subjected to a condensation polymerization reaction at a temperature of 170°C to 230°C in a nitrogen environment, and mechanically stirred at a rotation speed of 150rpm. At the same time, the moisture generated during the reaction was removed, and the outlet of the moisture was removed. The temperature is controlled at 80°C to 120°C. When the acid value is lower than 40mgKOH/g, start to cool down to 80℃, and add 490 grams of styrene and 1 gram of hydroquinone to obtain 1227 grams of light yellow transparent substance with a viscosity of 300 cps, which is halogen-free Flame-retardant unsaturated polyester.

Preparation Example 3 Halogen-free flame-retardant unsaturated polyester

The weight ratio is 1:1:0.364:1.24:1.24 maleic anhydride, phthalic anhydride, [(6-oxo-6H-dibenzo[C,E][1,2]oxaphosphine Cyclo-6-yl)methyl]succinic acid {[(6-Oxido-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)methyl]butanedioic acid, CAS accession number 63562-33- 4}, Diethylene glycol and ethylene glycol are mixed, and the mixture is configured to have a total weight of 800 grams. The mixture was subjected to a condensation polymerization reaction at a temperature of 170°C to 230°C in a nitrogen environment, and mechanically stirred at a rotation speed of 150rpm. At the same time, the moisture generated during the reaction was removed, and the outlet of the moisture was removed. The temperature is controlled at 80°C to 120°C. When the acid value is lower than 40mgKOH/g, start to cool down to 80℃, and add 490 grams of styrene and 1 gram of hydroquinone to obtain 1227 grams of light yellow transparent substance with a viscosity of 300 cps, which is halogen-free Flame-retardant unsaturated polyester.

Preparation Example 4 Halogen-free unsaturated polyester

Mix maleic anhydride, phthalic anhydride, diethylene glycol, and ethylene glycol in a weight ratio of 1:1:1.05:1.05 to form a mixture with a total weight of 800 grams. The mixture was subjected to a condensation polymerization reaction at a temperature of 170°C to 230°C in a nitrogen environment, and mechanically stirred at a rotation speed of 150rpm. At the same time, the moisture generated during the reaction was removed, and the outlet of the moisture was removed. The temperature is controlled at 80°C to 120°C. When the acid value is lower than 40mgKOH/g, start to cool down to 80℃, and add 490 grams of styrene and 1 gram of hydroquinone to obtain 1227 grams of light yellow transparent substance with a viscosity of 300 cps, which is halogen-free Flame-retardant unsaturated polyester.

Table 1 Halogen-free flame-retardant unsaturated polyester Preparation example 1 2 3 4 Phosphorus-containing flame-retardant monomer represented by formula (I) (g) Groups containing dihydroxy 30 6 0 0 Groups containing dicarboxylic acid groups 0 0 60 0 Dosage (wt%) 3.75 0.75 7.5 0 Alcohol component Organic polyol (g) Diethylene glycol 193 203 205 205 Ethylene glycol 193 203 205 205 Acid component Unsaturated polybasic acid anhydride (g) maleic anhydride 192 194 165 195 Phthalic Anhydride 192 194 165 195 Condensation polymerization Temperature(℃) 170～230 170～230 170～230 170～230 Time (hour) 20hr 20hr 20hr 20hr Acid value (mgKOH/g) ＜40 ＜40 ＜40 ＜40 Dilute monomer Styrenic monomer Styrene (g) 490 490 490 490 Inhibitor Hydroquinone (g) 1 1 1 1

Example 1

250 grams of the halogen-free flame-retardant unsaturated polyester of Preparation Example 1 and 250 grams of aluminum hydroxide were thoroughly stirred and mixed, and then 5 grams of ketone peroxide was added to form a coating. The paint was applied to a glass fiber cloth with a length of 30 cm, a width of 30 cm and a thickness of 0.1 cm, and the glass fiber cloth was impregnated and wetted. Then, another glass fiber cloth was stacked, and then the paint was used for coating Brush, stacking and painting repeatedly, a total of 5 times. Then, it was placed at 25°C for 48 hours of curing reaction to obtain a halogen-free flame-retardant fiber-reinforced plastic board with a thickness of 0.6 cm, wherein the total amount of the halogen-free flame-retardant fiber-reinforced plastic board was 100% by weight. The amount of the glass fiber is 50 wt%.

Examples 2 to 6 and Comparative Examples 1 to 5

Examples 2 to 6 and Comparative Examples 1 to 5 were carried out in the same steps as in Example 1, with the main difference being that the amount of each component was changed.

Evaluation item

Oxygen index (OI) test: the panels of Examples 1 to 6 and Comparative Examples 1 to 5 were ignited with an igniter in an environment containing a mixed gas of oxygen and nitrogen, and the test was able to support the panels The lowest oxygen volume concentration during continuous combustion. The judgment standard is that an oxygen index greater than 27vol% indicates flame retardancy, an oxygen index of 22vol% to 27vol% indicates flammability, and an oxygen index less than 22vol% indicates flammability.

Smoke toxicity test: The panels of Examples 1 to 6 and Comparative Examples 1 to 5 were measured in accordance with the smoke density (Ds) test method ASTM E662. ○ means that Ds(1.5min)≤100 and Ds(4.0min)≤200 are satisfied; X means that Ds(1.5min)≤100 or Ds(4.0min)≤200 is not satisfied.

Bending strength test: The plates of Examples 1 to 6 and Comparative Examples 1 to 5 were measured in accordance with ASTM D790-15, the standard test method for bending properties of unreinforced and reinforced plastics and electrical insulating materials.

Table 2 Plate Example 1 2 3 4 5 6 Halogen-free flame-retardant unsaturated polyester resin Preparation example 1 3 1 1 1 1 Dosage (wt%) 25 25 twenty two 10 30 15 Filler Aluminum hydroxide (wt%) 25 25 28 40 35 15 fiber Glass fiber (wt%) 50 50 50 50 35 70 Evaluation item Oxygen index (vol%) 46 49 47 57 33 56 Smoke toxicity 1.5 minutes Ds 2.4 1.9 2.0 0.9 5.5 1.1 4 minutes Ds 54.4 45.8 47.5 20.2 54.2 25.3 result ○ ○ ○ ○ ○ ○ Flexural strength (MPa) 569 563 539 302 203 612

table 3 Plate Comparative example 1 2 3 4 5 Halogen-free flame-retardant unsaturated polyester resin Preparation example 2 4 1 1 1 Dosage (wt%) 25 25 38 50 45 Filler Aluminum hydroxide (wt%) 25 25 12 0 40 fiber Glass fiber (wt%) 50 50 50 50 15 Evaluation item Oxygen index (vol%) 36 32 35 28 29 Smoke toxicity 1.5 minutes Ds 22.5 53.1 22.6 91.5 26.5 4 minutes Ds 235 301 241 422 243 result X X X X X Flexural strength (MPa) 575 565 623 659 102

From the experimental data of Examples 1 to 6 in Table 2, it can be seen that the phosphorus-containing flame-retardant monomer represented by formula (I) is used in the halogen-free flame-retardant composition of the present invention, and the amounts of these components are all in the amount described in the present invention. Within the range, the oxygen index is above 33vol% and the smoke toxicity test is passed, which means that the halogen-free flame-retardant fiber-reinforced plastic panel of the present invention is not easy to burn but has excellent flame retardancy, and is easy to self-extinguish after burning. In addition, low smoke The density is more beneficial for evacuation and extinguishing of fire.

In contrast to the halogen-free flame-retardant compositions of Comparative Examples 1 to 5, from the experimental data of Comparative Examples 1 to 5 in Table 3, it can be seen that the phosphorus-containing flame-retardant monomer represented by formula (I) is not used, or the amount of ingredients is not in this Within the scope of the invention, it is impossible to have both the oxygen index and smoke toxicity, and even the oxygen index and smoke toxicity are not good. This means that the plate is easy to burn and is not easy to self-extinguish after burning. Moreover, high smoke density is not In the event of a fire, evacuation and fire fighting are more disadvantageous.

In summary, by using the phosphorus-containing flame-retardant monomer represented by formula (I) and matching the amount of each component, the halogen-free flame-resistant composition can make halogen-free flame-resistant fiber reinforced plastic panels have high oxygen index and low smoke Toxicity, it can indeed achieve the purpose of the invention.

However, the above are only examples of the present invention. When the scope of implementation of the present invention cannot be limited by this, all simple equivalent changes and modifications made in accordance with the scope of the patent application of the present invention and the content of the patent specification still belong to Within the scope of the patent for the present invention.

no.

Claims (9)

A halogen-free flame-retardant composition comprising: a halogen-free flame-retardant unsaturated polyester, which is formed by the reaction of a reaction composition containing a phosphorus-containing flame-retardant monomer represented by formula (I), an alcohol component, and an acid component , Wherein the acid component includes at least one of a polybasic acid and a polybasic acid anhydride, and the sum of the amounts of the phosphorus-containing flame-retardant monomer represented by the formula (I), the alcohol component and the acid component is 100wt% In total, the amount of the phosphorus-containing flame-retardant monomer represented by the formula (I) is greater than 0.75wt% and less than 7.5wt%,

Formula (I) R represents a dihydroxy-containing group or a dicarboxylic acid group-containing group; fillers; and fibers; wherein, based on the total amount of the halogen-free flame-retardant fiber-reinforced plastic board, the The amount of halogen flame-retardant unsaturated polyester is 10wt% to 38wt%, and the amount of filler is greater than 12wt% and 40wt% or less. The halogen-free flame-resistant composition according to claim 1, wherein, based on the total amount of the halogen-free flame-resistant fiber-reinforced plastic board being 100 wt%, the amount of the fiber is 15 wt% to 70 wt%. The halogen-free flame-resistant composition according to claim 1, wherein the dihydroxy-containing group is

, Wherein R ¹ , R ² and R ³ represent an alkyl group. The halogen-free flame retardant composition according to claim 1, wherein the group containing a dicarboxylic acid group is

, Where R ⁴ represents an alkyl group. The halogen-free flame-retardant composition according to claim 1, wherein the reaction composition further includes a diluting monomer, and the diluting monomer includes at least one of a styrene-based monomer and an acrylate-based monomer. The halogen-free flame-resistant composition according to claim 1, wherein the filler is selected from aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, silicon dioxide, calcium carbonate, titanium dioxide, graphite, magnesium carbonate, and molybdenum trioxide , Zinc borate, zinc stannate, or any combination of the above. The halogen-free flame-resistant composition according to claim 1, wherein the fiber is selected from glass fiber, carbon fiber, silicon carbide fiber, boron fiber, aramid fiber, ceramic fiber, or any combination of the foregoing. The halogen-free flame-retardant composition according to claim 1, further comprising a hardener. A halogen-free flame-resistant fiber-reinforced plastic board is formed from the halogen-free flame-resistant composition according to any one of claims 1 to 8.