CN107880257B - Flame-retardant material with high refractive index, manufacturing method thereof and flame-retardant polymer with high refractive index - Google Patents
Flame-retardant material with high refractive index, manufacturing method thereof and flame-retardant polymer with high refractive index Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 95
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- 125000003367 polycyclic group Chemical group 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 25
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- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 4
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
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- 229910052787 antimony Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention provides a method for manufacturing a flame-retardant material with high refractive index, which comprises the following steps: polymerizing dicarboxylic acid, alkylene glycol, poly-phenylene glycol and a first poly-phenylene ester flame retardant to form a polymer, wherein the dicarboxylic acid is 50 to 65 parts by weight, the alkylene glycol is 20 to 30 parts by weight, the poly-phenylene glycol is 9 to 15 parts by weight, and the first poly-phenylene ester flame retardant is 1 to 4 parts by weight; and a mixed polymer and a second polyphenyl cyclic ester flame retardant, wherein the second polyphenyl cyclic ester flame retardant is 4-10 parts by weight. The flame retardant material is an environment-friendly halogen-free flame retardant and has the advantages of high refractive index, good flame retardance and good heat resistance.
Description
Technical Field
The present invention relates to a flame retardant material having a high refractive index, a method for manufacturing the same, and a flame retardant polymer having a high refractive index, and more particularly, to a method for manufacturing a flame retardant material by polymerizing dicarboxylic acid, alkylene glycol, poly-phenylene glycol, and a first poly-phenylene ester flame retardant to form a flame retardant polymer, and then mixing the flame retardant polymer with a second poly-phenylene ester flame retardant.
Background
The flame retardant is an auxiliary agent capable of improving the flame retardancy of inflammable matters or inflammable matters, so that the effects of preventing the inflammable matters and the inflammable matters from being ignited and inhibiting flame from spreading are achieved, and the safety of the process of using the material is ensured. Among the various flame retardants, the halogen-based flame retardant has the advantages of high flame retardant efficiency, excellent flame retardant performance and low cost, and thus is the most widely used flame retardant. However, halogen-based flame retardants generate a large amount of smoke and corrosive toxic gases (e.g., hydrogen halide gas) during thermal cracking or combustion, and are a considerable environmental hazard.
For environmental reasons, the halogen-based flame retardant should be replaced with other types of non-toxic flame retardants, such as phosphorus-based flame retardants, antimony-based flame retardants, aluminum hydroxide flame retardants, or magnesium hydroxide flame retardants. However, these flame retardants still have some drawbacks, such as: poor thermal stability, susceptibility to hydrolysis, or high volatility, which limits its use. In addition, when these flame retardants are used in optical components requiring flame retardancy, there is a problem that transparency, transmittance and structural design of the optical components are adversely affected due to low refractive index and yellowish color of the flame retardants.
In view of the above, a new flame retardant material and a method for manufacturing the same are needed to solve the above problems.
Disclosure of Invention
An object of the present invention is to provide a novel flame retardant material and a method for manufacturing the same, which can substantially solve the above problems of the prior art.
The invention provides a method for manufacturing a flame-retardant material with high refractive index, which comprises the following steps:
polymerizing dicarboxylic acid, alkylene glycol, poly-phenylene glycol and a first poly-phenylene ester flame retardant to form a polymer, wherein the dicarboxylic acid is 50 to 65 parts by weight, the alkylene glycol is 20 to 30 parts by weight, the poly-phenylene glycol is 9 to 15 parts by weight, and the poly-phenylene ester flame retardant has a chemical formula shown in formula (1):
the first polyphenyl cyclic ester flame retardant is 1-4 parts by weight and has a chemical formula shown as a formula (2):
wherein x is 24 to 30; and
mixed polymer and a second polyphenyl cyclic ester flame retardant, wherein the second polyphenyl cyclic ester flame retardant is 4-10 parts by weight and has a chemical formula shown as a formula (2).
In one embodiment, the total phosphorus content in the dicarboxylic acid, alkylene glycol, polyphenyl cyclic glycol, and first polyphenyl ester flame retardant is 1000ppm to 3500 ppm.
In one embodiment, the phosphorus content in the polymer and the second polycyclic ester flame retardant is at least 6800 ppm.
In one embodiment, the dicarboxylic acid, alkylene glycol, poly (phenylene glycol), and first poly (phenylene ester) flame retardant are polymerized at a temperature of 220 ℃ to 250 ℃.
In one embodiment, the dicarboxylic acid, alkylene glycol, poly (phenylene glycol), and first poly (phenylene ester) flame retardant have a polymerization time of 150 minutes to 200 minutes.
In one embodiment, the dicarboxylic acid is Terephthalic acid (TPA).
In one embodiment, the alkylene glycol is Ethylene Glycol (EG).
The invention provides a flame-retardant polymer with high refractive index, which has a chemical formula shown as a formula (3):
wherein x is 24 to 30, m and n are 50 to 200, respectively, and p is 1 to 5.
The present invention provides a flame retardant material having a high refractive index, comprising: a flame retardant polymer having a high refractive index; and a polycyclic ester flame retardant having a chemical formula shown in formula (2):
wherein x is 24 to 30.
In one embodiment, the phosphorus content in the flame retardant material having a high refractive index is 6800ppm to 7500 ppm.
Compared with the prior art, the flame-retardant material and the flame-retardant polymer are environment-friendly halogen-free flame retardants, so that toxic gas is not released in the combustion process, and the flame-retardant material and the flame-retardant polymer have the advantages of high refractive index, good flame retardance and good heat resistance, so that the flame-retardant material and the flame-retardant polymer are quite wide in application.
Drawings
The above and other aspects, features and other advantages of the present invention will become more apparent by referring to the content of the specification in conjunction with the accompanying drawings, in which:
FIG. 1 is a flow chart illustrating a method for manufacturing a flame retardant material with a high refractive index according to an embodiment of the present invention; and
FIG. 2 is a graph showing experimental results of variation of voltage supplied for maintaining a constant rotation speed of a stirring rod in a reaction tank with polymerization time in the process of manufacturing a flame retardant polymer;
wherein, the notation:
100: manufacturing method
110. 120: operation of
210. 220, and (2) a step of: data points.
Detailed Description
The following disclosure provides many different embodiments, or examples, for implementing different features of the invention. The composition and layout of specific examples are described below to simplify the present disclosure. These are, of course, merely examples and are not intended to be limiting.
In order to solve the problems described in the prior art, the present invention provides a flame retardant material and a method for manufacturing the same, wherein the flame retardant material comprises a flame retardant polymer. The flame-retardant material and the flame-retardant polymer are environment-friendly halogen-free flame retardants, so that toxic gases are not released in the combustion process, and the flame-retardant material and the flame-retardant polymer have the advantages of high refractive index, good flame retardance and good heat resistance, so that the flame-retardant material and the flame-retardant polymer are quite wide in application. For example, the flame retardant material and the flame retardant polymer can be used in an optical component to make the optical component thin due to the advantage of high refractive index.
The method of making a flame retardant material comprises the steps of: preparing dicarboxylic acid, alkylene glycol, polyphenyl diol and polyphenyl ester flame retardant, copolymerizing a part of polyphenyl ester flame retardant with dicarboxylic acid, alkylene glycol and polyphenyl diol to form flame retardant polymer, and then adding the rest polyphenyl ester flame retardant and the flame retardant polymer to blend to form the flame retardant material.
The detailed manufacturing steps are described below with reference to FIG. 1.
Fig. 1 illustrates a method 100 for manufacturing a flame retardant material with a high refractive index, which includes operations 110 and 120. In operation 110, a dicarboxylic acid, an alkylene glycol, a poly-phenylene glycol, and a first poly-phenylene ester flame retardant are polymerized to form a flame retardant polymer, wherein the dicarboxylic acid is 50 to 65 parts by weight, the alkylene glycol is 20 to 30 parts by weight, the poly-phenylene glycol is 9 to 15 parts by weight, and the first poly-phenylene ester flame retardant is 1 to 4 parts by weight. In detail, the polycyclic aromatic diol has a chemical formula shown in formula (1):
the chemical name of the compound is 9, 9-bis- [ (4-hydroxyethoxy) phenyl ] fluorene (BPEF); the first polycyclic ester flame retardant has a chemical formula shown as formula (2):
wherein x is 24 to 30. In one embodiment, the first polycyclic Ester flame retardant is commercially available from Sanko Co., Ltd., Japan under the trade name M-Ester bioconjugation (ME-P8).
Since the dicarboxylic acid has carboxyl (-COOH) groups at both ends, and the alkylene glycol, the polycyclic diol and the first polycyclic ester flame retardant all have two hydroxyl (-OH) groups, the reactants undergo esterification reaction and are copolymerized to form the flame retardant polymer. With the difference in the weight ratio between the dicarboxylic acid, alkylene glycol, poly (phenylene glycol) and the first poly (phenylene ester) flame retardant, the weight ratio of each monomer unit in the flame retardant polymer will also be different. For example, if the weight ratio of the dicarboxylic acid, alkylene glycol, poly (phenylene glycol) and first poly (phenylene ester) flame retardant is 1:2:3:4, the weight ratio of the monomer units in the flame retardant polymer formed from the dicarboxylic acid, alkylene glycol, poly (phenylene glycol) and first poly (phenylene ester) flame retardant will also be close to 1:2:3: 4.
In one embodiment, the dicarboxylic acid is Terephthalic acid (TPA) and the alkylene glycol is Ethylene Glycol (EG), and thus the flame retardant polymer produced from the dicarboxylic acid, the alkylene glycol, the poly (phenylene glycol), and the first poly (phenylene ester) flame retardant has a chemical formula shown in formula (3):
wherein x is 24 to 30, m and n are 50 to 200, respectively, and p is 1 to 5. However, it is also possible to form other copolymers of terephthalic acid, ethylene glycol, poly (phenylene glycol) and the first poly (phenylene ester) flame retardant at the same time as the flame retardant copolymer is formed. For example, polyethylene terephthalate (PET), a polymer copolymerized from terephthalic acid and a polycyclic diol, a polymer copolymerized from terephthalic acid and a first polycyclic ester flame retardant, and the like may be formed.
Because the poly-benzene ring diol and the first poly-benzene ring ester flame retardant have benzene ring structures, the flame retardant polymer contains the benzene ring structures and has high refractive index. In detail, the first polycyclic ester flame retardant contains phosphorus (P), which is a phosphorus flame retardant having the following flame retardant mechanism: in the combustion process, the carbon-phosphorus bond in the first polyphenyl cyclic ester flame retardant is broken to form a compound with a chemical formula shown as a formula (4),
next, this compound is further decomposed to form phosphoric acid (metaphosphoric acid), which is then dehydrated to form metaphosphoric acid (HPO)3)n) The metaphosphoric acid is a stable polymer, has strong dehydration property, and can cover the surface of combustible materials or inflammable materials to isolate external oxygen from entering and prevent internal combustible gas from overflowing, so as to achieve the flame retardant effect, and the flame retardant effect of the flame retardant is in direct proportion to the phosphorus content in the flame retardant. The first poly (phenylene ester) flame retardant is a high molecular flame retardant, and the thermal cracking temperature is about 362.1 ℃, so that the thermal cracking is not easy to occur in the polyester reaction process. Since the heat resistance is better than that of a general low molecular weight flame retardant, phosphorus contained in the first polycyclic ester flame retardant forms a flame retardantCan remain in the flame-retardant polymer with little loss during the process of burning the polymer. Because the flame-retardant polymer also has a structure similar to that of the first polyphenyl cyclic ester flame retardant, the flame-retardant polymer can break carbon-phosphorus bonds according to the flame-retardant mechanism to form metaphosphoric acid so as to prevent external oxygen from reacting with combustible substances or inflammable substances and prevent combustible gases in the combustible substances or inflammable substances from overflowing, thereby having good flame-retardant effect. In addition, the benzene ring structure in the flame-retardant polymer can not only enable the flame-retardant polymer to have high refractive index, but also improve the carbon forming property of the flame-retardant polymer, thereby improving the flame-retardant effect of the flame-retardant polymer.
However, it is particularly noted that, since the first polycyclic ester flame retardant is a high molecular type flame retardant, when the first polycyclic ester flame retardant is copolymerized with other reactants, the polymerization effect is poor and a long polymerization time is required, and therefore, the ratio of the first polycyclic ester flame retardant to the other reactants must be adjusted to achieve the optimal polymerization effect. In one embodiment, the dicarboxylic acid, alkylene glycol, poly (phenylene glycol) and the first poly (phenylene ester) flame retardant have a total phosphorus content of 1000ppm to 3500ppm, and when the total phosphorus content is adjusted to fall within this range, the dicarboxylic acid, alkylene glycol, poly (phenylene glycol) and the first poly (phenylene ester) flame retardant have a good polymerization effect and can react rapidly to form a flame-retardant polymer.
The polymerization conditions can be adjusted depending on the amount of the reactants used. In one embodiment, the dicarboxylic acid, alkylene glycol, poly (phenylene glycol), and first poly (phenylene ester) flame retardant are polymerized at a temperature, for example, of 220 ℃ to 250 ℃ for a polymerization time, for example, of 150 minutes to 200 minutes.
Next, in operation 120, a flame retardant polymer and a second polybenzoate flame retardant are mixed to form a flame retardant material, wherein the second polybenzoate flame retardant is 4 to 10 parts by weight and also has a chemical formula as shown in formula (2). In operation 120, the second polycyclic ester flame retardant does not chemically react with the flame retardant polymer, and both are present as a mixture. As mentioned above, the second poly (phenylene ester) flame retardant itself has good flame retardancy, so that the phosphorus content of the flame retardant material of the present invention can be increased by the operation 120, so as to achieve the effect of improving the flame retardancy.
In summary, the method of manufacturing the flame retardant material of the present invention comprises two operations. In operation 110, a quantity of the polycyclic ester flame retardant is added to copolymerize with the dicarboxylic acid, alkylene glycol, and polycyclic diol, and the weight ratio of the reactants is adjusted to allow the copolymerization to form more polymer in a shorter reaction time. Next, in operation 120, some other polyphenyl ring ester flame retardants capable of improving flame retardancy are added to blend with the polymer, and the flame retardant material is formed by adding the polyphenyl ring ester flame retardants in two stages, so that the problem that the polymer type polyphenyl ring ester flame retardants need longer polymerization time is solved.
Finally, when the flame retardant material is analyzed, the flame retardancy of the flame retardant material is evaluated according to the plastic flammability standard UL94 issued by Underwriters Laboratories, USA, when the phosphorus content in the flame retardant material is at least 6800ppm, and the flame retardancy of the flame retardant material can reach a relatively excellent V0 rating. The V0 rating represents that in the case of vertical burning, the sample would stop burning within 10 seconds and allow for non-burning particles to accompany the dripping. In general, the flame retardant material of V0 grade can provide quite good flame retardant effect for products. Therefore, the amounts of the dicarboxylic acid, the alkylene glycol, the polycyclic benzene glycol, the first polycyclic benzene ester flame retardant and the second polycyclic benzene ester flame retardant can be adjusted according to the finally required flame retardant effect, the phosphorus content in the flame retardant material is not limited to be at least 6800ppm, and the higher the phosphorus content in the flame retardant material is, the better the flame retardancy is. The phosphorus content in the flame retardant material having a high refractive index may be, for example, 6800ppm to 7500ppm in consideration of cost.
Typical commercially available optical plastics have refractive indices of about 1.4 to 1.6. For example, polymethyl methacrylate (PMMA) has a refractive index of about 1.49; polyethylene terephthalate (PET) has a refractive index of about 1.56 to 1.57. However, the refractive index of the flame retardant material of the present invention can be as high as 1.65, which exceeds the refractive index of the general commercially available optical plastics, so that the flame retardant material of the present invention is suitable for manufacturing optical components. When the optical components (such as an optical lens module, a plastic lens, an optical film or an optical fiber) are made of materials with higher refractive index, the optical components can be designed to be thinner and lighter, so that the flame retardant material of the invention not only meets the market demand, but also has wider application.
The following examples are presented to illustrate specific aspects of the present invention and to enable those of ordinary skill in the art to practice the invention. The following examples should not be construed as limiting the invention.
Experimental example 1: observing the reaction process of forming the flame-retardant polymer by the terephthalic acid, the ethylene glycol and the polyphenyl cyclic ester flame retardant
This example uses Terephthalic acid (TPA), Ethylene Glycol (EG) and a polycyclic Ester flame retardant, which is commercially available from Sanguang, Japan under the trade name of M-Ester Polycondensation (ME-P8), as reactants. The reaction of the above reactants in forming the flame retardant polymer was observed. In this experimental example, no polycyclic diol was added to the reaction mixture because the molecular weight of the polycyclic diol was much smaller than that of the polycyclic ester flame retardant, and therefore the presence or absence of the polycyclic diol in the reaction mixture did not greatly affect the molecular weight of the finally formed flame retardant polymer. Thus, the reaction process of forming a flame retardant polymer using terephthalic acid, ethylene glycol, a polyphenyl diol and a polyphenyl ester flame retardant as reactants can be inferred by observing the reaction process of forming a flame retardant polymer using terephthalic acid, ethylene glycol and a polyphenyl ester flame retardant as reactants.
In this experimental example, two reactions were observed to form a flame retardant polymer with reactants having different total phosphorus contents, and example one and example two represent two different manufacturing processes, in example one, the reactants used comprised terephthalic acid, ethylene glycol and ME-P8, and the total phosphorus content was 7000 ppm. In example two, the reactants used comprised terephthalic acid, ethylene glycol and ME-P8, and the total phosphorus content was 3500 ppm. The reactants of the first and second examples were placed in reaction tanks, respectively, and polymerization was carried out to form a flame retardant polymer.
Referring to FIG. 2, FIG. 2 shows the experimental results of the variation of the voltage required to maintain the stirring rod in the reaction tank at a constant rotation speed with the polymerization time in the process of manufacturing the flame retardant polymer, in which the horizontal axis represents the polymerization time (minutes) and the vertical axis represents the voltage (kV) required to maintain the stirring rod in the reaction tank at a constant rotation speed. In the polymerization reaction of terephthalic acid, ethylene glycol, and a polycyclic ester flame retardant, it is necessary to uniformly mix the above reactants by a stirring rod, and the amount of the polymer produced increases as the polymerization reaction time increases. Since the viscosity of the mixture in the reaction tank increases due to the higher molecular weight of the polymer, when the amount of the polymer is increased, a higher voltage must be applied to provide a higher torque to rotate the stirring rod so as to maintain the rotation speed of the stirring rod constant. Therefore, the completion degree of the polymerization reaction can be judged by estimating the amount of the polymer in the reaction vessel from the voltage value. As can be understood from FIG. 2, as a result of an experiment in which the amount of polymer formed in the reaction vessel during the production of the flame-retardant polymer varies with the polymerization reaction time, the higher the voltage, the more the amount of polymer formed in the reaction vessel, and the lower the voltage, the less the amount of polymer formed in the reaction vessel.
Referring to fig. 2, data points 210 and 220 are data points measured by polymerizing the reactants of the first embodiment and the second embodiment, respectively, and it can be seen from fig. 2 that in the data points 210 and 220, as the polymerization time increases, the voltage also increases, indicating that the flame retardant polymer is gradually generated in the reaction tank. Of particular note, example two is capable of producing more flame retardant polymer than example one, within the same polymerization time. For example, at a polymerization time of about 180 minutes, the voltage at data point 210 is about 195kV and the voltage at data point 220 is about 260 kV. Therefore, it is found that when the total phosphorus content of the reactants is adjusted to 3500ppm, the efficiency of converting terephthalic acid, ethylene glycol, and the polycyclic ester flame retardant into the flame retardant polymer is quite good. In reverse example one, the reaction time is longer than 150 minutes to form the flame retardant polymer due to the addition of too much polycyclic ester flame retardant.
Next, the polymerization time was about 180 minutes, and the flame retardant material in the reaction tank, which contained the flame retardant polymer formed and possibly some unreacted reactants, was subjected to a property test. In detail, the flame retardant materials formed in the first and second examples were tested for Intrinsic viscosity (Intrinsic viscosity), Glass transition temperature (Tg), melting point (Tm), and acid value, and the results are shown in table one:
watch 1
| Example one | Example two | |
| Phosphorus content (ppm) | 7000 | 3500 |
| Intrinsic viscosity | 0.428 | 0.620 |
| Tg(℃) | 70.0 | 71.0 |
| Tm(℃) | 239.7 | 240.1 |
| Acid value (mu eq/g) | 98 | 30 |
Generally, the more high molecular weight compounds the more the flame retardant material contains, the greater the intrinsic viscosity, and thus the number of flame retardant polymers contained in the flame retardant material can be determined by the intrinsic viscosity values listed in table one. From the table one, the intrinsic viscosity of the flame retardant material formed by the example one is lower than that of the flame retardant material formed by the example two, which means that the flame retardant material formed by the example two contains more flame retardant polymer. And, the intrinsic viscosity of the second embodiment is higher than 0.5 and the melting point is 240.1 ℃, which means that the flame retardant material meets the requirement of general industry and can be used for manufacturing general optical components. In addition, the acid value of the flame retardant material formed by the first example is higher than that of the flame retardant material formed by the second example, which means that the flame retardant material formed by the first example contains more unreacted terephthalic acid. On the other hand, the acid value of the flame retardant material formed by example two was 30. mu. eq/g, which means that the terephthalic acid in the reactants was almost completely reacted. Thus, this experiment demonstrates that the efficiency of converting reactants to flame retardant polymers is better if the polymerization is carried out with reactants having a phosphorus content of about 3500 ppm.
Experimental example 2: property testing of flame retardant materials polymerized from reactants having different total phosphorus content
In this experimental example, two other flame retardant materials polymerized from reactants having different total phosphorus contents were tested for properties, wherein two different manufacturing methods were used in the third and fourth examples. In example three, the reactants used comprised terephthalic acid (TPA), Ethylene Glycol (EG), and ME-P8, with a total phosphorus content of 3500 ppm; in example four, the reactants used comprised terephthalic acid, ethylene glycol and ME-P8, with a total phosphorus content of 4500 ppm. The reactants of the third and fourth examples are put into the reaction tank respectively, and polymerization is carried out to form the flame retardant material, and besides the flame retardant polymer, the flame retardant material may also contain some unreacted reactants. Next, the intrinsic viscosity, glass transition temperature (Tg), melting point (Tm), and acid value of the flame retardant material were measured, and the results are shown in table two:
watch two
| EXAMPLE III | Example four | |
| TPA(wt％) | 66.10 | 65.23 |
| EG(wt％) | 29.62 | 29.06 |
| ME-P8(wt％) | 4.28 | 5.71 |
| Phosphorus content (ppm) | 3500 | 4500 |
| Intrinsic viscosity | 0.618 | 0.413 |
| Tg(℃) | 71.0 | 70.0 |
| Tm(℃) | 240.5 | 239.8 |
| Acid value (mu eq/g) | 32 | 95 |
From table two, the intrinsic viscosity of the flame retardant material formed by example four is lower than that of the flame retardant material formed by example three, which means that the flame retardant material formed by example three contains more flame retardant polymers, and the intrinsic viscosity is higher than 0.5 and the melting point is 240.5 ℃, which means that the flame retardant material meets the requirements of general industry and can be used for manufacturing general optical components. In addition, the acid value of the flame retardant material formed by the fourth example was higher than that of the flame retardant material formed by the third example, which means that the flame retardant material formed by the fourth example contained much unreacted terephthalic acid, while the acid value of the flame retardant material formed by the third example was 32. mu. eq/g, which means that the terephthalic acid in the reactant was almost completely reacted.
It is noted that the total phosphorus content of example four is only slightly higher than that of example three, which results in poor polymerization effect among the terephthalic acid, ethylene glycol, and the polycyclic ester flame retardant in example four, and thus the intrinsic viscosity of the flame retardant material formed by example four is low and the acid value is high. This example again demonstrates the superior efficiency of converting terephthalic acid, ethylene glycol, and the polyphenyl ester flame retardants to flame retardant polymers at a total phosphorus content of 3500 ppm.
Experimental example 3: the property test is carried out on the flame-retardant materials polymerized by different reactants and different manufacturing methods
In this experimental example, the properties of the flame retardant materials polymerized from the reactants of six different components were tested, wherein six different manufacturing methods were used in comparative examples one to four and examples five to six, respectively, and the various components and test results of the flame retardant materials are shown in table three. In detail, the reaction processes of comparative examples one to four are all to mix all the reactants uniformly and then perform esterification reaction to form the flame retardant material (possibly including some unreacted reactants), wherein the flame retardant of comparative examples two and three are added at one time. In addition, the reactants of the second and third comparative examples respectively include conventional phosphorus flame retardants CEPPA and DOPO-IT, and during the esterification process, part of the flame retardants may be consumed during the reaction process, so that the phosphorus content of the final product (flame retardant material) is reduced. For the property test of the reactant components and the flame retardant material in comparative examples one to four, please refer to table three.
In example five, the reactants used comprised terephthalic acid, ethylene glycol and flame retardant ME-P8, with a total phosphorus content of 7000 ppm. The esterification reaction procedure of example 5 was as follows: mixing terephthalic acid, ethylene glycol and part of the flame retardant ME-P8, the total phosphorus content being 3500ppm, polymerizing the reactants to form a flame retardant polymer; next, the flame retardant polymer and the remaining polycyclic ester flame retardant are mixed to form the final flame retardant material. It is noted that the flame retardant of example five is added in a second addition. During the reaction, part of the polycyclic ester flame retardant may be consumed during the reaction, so that the phosphorus content of the finally formed product (flame retardant material) is reduced. For the property test of the reactant components and the flame retardant material of example five, please refer to table three.
In example six, the reactants used comprised terephthalic acid, ethylene glycol, poly-benzene cyclic diol, and flame retardant ME-P8, with the total phosphorus content of the reactants being 7000 ppm. The esterification reaction procedure for example six was as follows: mixing terephthalic acid, ethylene glycol, poly (phenylene glycol) and part of the flame retardant ME-P8, the total phosphorus content being 3500ppm, polymerizing the reactants to form a flame retardant polymer; next, the flame retardant polymer and the remaining polycyclic ester flame retardant are mixed to form the final flame retardant material. It is noted that the flame retardant of the sixth embodiment is added twice. The properties of the reactant components and flame retardant materials of example six were tested as shown in Table three.
Watch III
From Table three, the refractive index of the flame retardant material of example six is as high as 1.6596, which is higher than that of the high refractive index materials commonly used in industry (such as polymethyl methacrylate and polyethylene terephthalate). The flame retardancy of the flame retardant material was evaluated according to the flammability standard of plastics UL94, and the flame retardancy of the flame retardant material of example six was a relatively good V0 rating. In addition, the intrinsic viscosity of the flame retardant material is higher than 0.5, and the melting point is 220.7 ℃. Therefore, it can be seen that in all the examples and comparative examples, the flame retardant material of the present invention has the highest refractive index and the most excellent flame retardancy, and the intrinsic viscosity and the melting point can also meet the requirements of general optical component manufacturing.
In addition, from the experimental data of the second, third and fifth comparative examples, in the fifth example, the phosphorus content of the reactant is 7000ppm, the phosphorus content of the product is 6910ppm, and the phosphorus loss is less than that of the second and third comparative examples, which proves that the phosphorus loss during the esterification reaction can be reduced by selecting the flame retardant ME-P8 with high molecular weight and good heat resistance as the reactant, so that the finally formed flame retardant material has good flame retardancy.
In summary, in the invention, by adding the polycyclic ester flame retardant in two stages, some polycyclic ester flame retardants, the dicarboxylic acid, the alkylene glycol and the polycyclic glycol are firstly made to form the flame retardant polymer with high refractive index, and then the polycyclic ester flame retardant capable of improving flame retardancy is further added to be blended with the flame retardant polymer, so that the problem that the macromolecular polycyclic ester flame retardant needs longer polymerization reaction time is solved, and the flame retardant material with high refractive index, good flame retardancy and good heat resistance is obtained. In addition, the flame-retardant material and the flame-retardant polymer do not contain halogen, so that a large amount of smoke and corrosive toxic gas can not be generated like a halogen flame retardant in the combustion process, and the environment is protected. Based on the advantages, the flame-retardant material and the flame-retardant polymer have wider application range than the common traditional high-refractive-index material and flame-retardant material.
Although the present invention has been described with reference to the above embodiments, other embodiments are possible. Therefore, the spirit and scope of the claimed subject matter should not be limited to the description of the embodiments contained herein.
It will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and it is intended that the scope of the invention be limited only by the terms of the appended claims.
Claims (10)
1. A method of making a flame retardant material having a high refractive index, comprising:
polymerizing a dicarboxylic acid, an alkylene glycol, a polyphenyl cyclic glycol and a first polyphenyl cyclic ester flame retardant to form a polymer, wherein the dicarboxylic acid is 50 to 65 parts by weight, the alkylene glycol is 20 to 30 parts by weight, the polyphenyl cyclic glycol is 9 to 15 parts by weight, and the polyphenyl cyclic glycol has a chemical formula shown in a formula (1):
the first polyphenyl cyclic ester flame retardant is 1-4 parts by weight and has a chemical formula shown as a formula (2):
wherein x is 24 to 30; and
mixing the polymer with a second polyphenyl cyclic ester flame retardant, wherein the second polyphenyl cyclic ester flame retardant is 4-10 parts by weight and has a chemical formula shown as a formula (2).
2. The production method according to claim 1, wherein the total phosphorus content in the dicarboxylic acid, the alkylene glycol, the polycyclic benzene glycol, and the first polycyclic benzene ester flame retardant is 1000ppm to 3500 ppm.
3. The manufacturing method according to claim 1, wherein the phosphorus content in the polymer and the second polycyclic ester flame retardant is at least 6800 ppm.
4. The production method according to claim 1, wherein the dicarboxylic acid, the alkylene glycol, the polycyclic diol, and the first polycyclic ester flame retardant are polymerized at a temperature of 220 ℃ to 250 ℃.
5. The production method according to claim 1, wherein a polymerization reaction time of the dicarboxylic acid, the alkylene glycol, the polycyclic diol, and the first polycyclic ester flame retardant is 150 to 200 minutes.
6. The production process according to claim 1, wherein the dicarboxylic acid is terephthalic acid.
7. The production method according to claim 1, wherein the alkylene glycol is ethylene glycol.
8. A flame retardant polymer having a high refractive index, characterized by having a chemical formula as shown in formula (3):
wherein x is 24 to 30, m and n are 50 to 200, respectively, and p is 1 to 5.
9. A flame retardant material having a high refractive index, comprising:
a flame retardant polymer having a high refractive index according to claim 8; and
the polyphenyl cyclic ester flame retardant has a chemical formula shown as a formula (2):
wherein x is 24 to 30.
10. The flame retardant material of claim 9, wherein the phosphorus content is 6800ppm to 7500 ppm.
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