CN109233290B - Preparation method of phosphorus-containing intrinsic flame-retardant silicone rubber - Google Patents
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Abstract
The invention discloses a preparation method of phosphorus-containing intrinsic flame-retardant silicone rubber, which is obtained by performing epoxidation modification on heat-vulcanized silicone rubber by adopting a reaction blending modification method and introducing a phosphorus-containing flame-retardant intermediate, wherein the prepared silicone rubber has good flame retardance, can reach the UL94-V0 combustion grade, has the properties of high efficiency, no halogen, no smoke, no toxicity, good elastic restoring force and the like, is suitable for the field of electric protection with harsh requirements, and provides high-reliability safety protection for electric parts.
Description
Technical Field
The invention belongs to the field of flame-retardant high polymer materials, and particularly relates to a preparation method of intrinsic phosphorus-containing flame-retardant silicone rubber.
Background
The silicone rubber is an organosilicon polymer with a silicon-oxygen bond as a main chain, the molecular main chain is formed by alternating silicon and oxygen atoms, two organic groups are usually connected to the silicon atoms, and a high-molecular elastomer is formed after vulcanization. The silicon rubber has excellent electrical property, and the electrical property of the silicon rubber is slightly influenced by temperature, so that the silicon rubber is an insulating high polymer material with excellent and stable performance. Silicone rubber has good electrical insulation and high resistivity, and the resistance value remains stable over a wide temperature range and frequency range. Silicone rubber has good resistance to high voltage corona discharge and arc discharge. Therefore, the silicon rubber is widely applied to the electric system of the fuel automobile and is mainly used in the fields of filling, sealing, connecting and the like.
The new energy power automobile is used as a substitute of the traditional fuel automobile, and an electric system of the new energy power automobile has the characteristics of large current, high voltage, alternating current and the like, so that new requirements on the performance of the silicon rubber are provided, namely the new energy power automobile has excellent flame retardant property. In order to obtain better flame retardant performance, a large amount of flame retardant such as magnesium hydroxide, aluminum hydroxide, melamine, bromide and the like is generally required to be added into the silicone rubber, but the excessive flame retardant causes the insulation, elasticity, strength and other properties of the silicone rubber to be greatly reduced or even lost. Therefore, the preparation of the high-performance intrinsic flame-retardant silicone rubber by selecting a suitable chemical synthesis or modification method has important practical significance. However, up to now, no report has been made on the preparation method of the intrinsic flame-retardant silicone rubber.
Disclosure of Invention
Aiming at the technical current situation, the invention provides a preparation method of intrinsic phosphorus-containing flame-retardant silicone rubber, which comprises the following steps:
adding raw silicone rubber into a vacuum kneader, and plasticating under a vacuum condition to prepare silicone rubber plasticated rubber; the raw silicone rubber is heat-vulcanized silicone rubber containing vinyl;
step (2) sequentially adding an organic peroxy acid epoxidation reagent and a metal oxide into the vacuum kneader in the step (1), and mixing the organic peroxy acid epoxidation reagent and the metal oxide with the silicone rubber plasticated rubber under a vacuum condition to enable vinyl of a silicone rubber molecular chain to react with a peroxy group of the epoxidation reagent to form an epoxidized group with high activity, so as to obtain epoxidized silicone rubber;
adding the phosphorus-containing flame retardant intermediate into the vacuum kneader in the step (2), mixing with the epoxidized silicone rubber under a vacuum condition, and reacting the phosphorus-containing flame retardant intermediate with the epoxidized silicone rubber in the mixing process to obtain primary phosphorus-containing intrinsic flame retardant silicone rubber;
and (4) adding the primary phosphorus-containing intrinsic flame-retardant silicone rubber into a rubber filter for filtering to remove impurities, thereby obtaining the phosphorus-containing intrinsic flame-retardant silicone rubber.
The raw silicone rubber comprises but is not limited to one or more of methyl vinyl silicone rubber (VMQ), methyl vinyl phenyl silicone rubber (PVMQ) and methyl vinyl trifluoropropyl silicone rubber (FVMQ).
The epoxidation reagent comprises one or more of but not limited to peroxyformic acid, peroxyacetic acid, peroxybenzoic acid, m-chloroperoxybenzoic acid and tert-butyl hydroperoxide.
The metal oxide includes but is not limited to one or more of zinc oxide, magnesium oxide and calcium oxide.
The phosphorus-containing flame retardant intermediate is preferably one or more of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof.
In the step (1), the plastication temperature is preferably 100-200 ℃, and more preferably 120-180 ℃.
In the step (1), the plastication time is preferably 20 to 60min, and more preferably 30 to 45 min.
In the step (1), the rotation speed of the rotor in the plastication process is preferably 40-200 rpm, and more preferably 80-120 rpm.
In the step (1), the hardness (Shore A) of the raw silicone rubber is preferably 20-60.
In the step (1), the raw silicone rubber preferably has a molar mass of 25X 104～70×104g/mol。
In the step (1), the preferable molar content of vinyl in the raw silicone rubber is 0.5-2.0%.
In the step (2), the mixing temperature is preferably 30 to 120 ℃, and more preferably 40 to 60 ℃.
In the step (2), the kneading time is preferably 30 to 180min, and more preferably 60 to 120 min.
In the step (2), the rotation speed of the rotor in the mixing process is preferably 20 to 100rpm, and more preferably 40 to 80 rpm.
In the step (2), preferably, the amount of the epoxidation reagent is 2-12 parts and the amount of the metal oxide is 3-15 parts based on 100 parts of the silicone rubber plasticated rubber by mass.
In the step (3), the mixing temperature is preferably 50 to 200 ℃, and more preferably 100 to 150 ℃.
In the step (3), the mixing time is preferably 60 to 300min, and more preferably 100 to 200 min.
In the step (3), the rotation speed of the rotor in the mixing process is preferably 40 to 120rpm, and more preferably 60 to 80 rpm.
In the step (3), preferably, the amount of the phosphorus-containing flame retardant intermediate is 5-35 parts by mass based on 100 parts by mass of the epoxidized silicone rubber.
In the step (3), a catalyst triphenylphosphine can be added to adjust the reaction rate, and the addition mass of the catalyst triphenylphosphine is preferably 0.5-10% of the mass of the phosphorus-containing flame retardant intermediate.
In the step (4), the mesh number of the filter screen of the rubber filter is preferably 60-500 meshes, and more preferably 300-500 meshes.
In the step (4), the preferable temperature of the material cylinder of the rubber filter is 30-150 ℃, and the further preferable temperature is 60-100 ℃.
Compared with the prior art, the invention adopts a reaction blending modification method to carry out epoxidation modification on the heat-vulcanized silicone rubber and introduce the phosphorus-containing flame-retardant intermediate to obtain the phosphorus-containing intrinsic flame-retardant silicone rubber, and has the following advantages:
(1) in the invention, metal oxide is added into the silicon rubber material, which not only can eliminate the adverse effect of the fatty acid by-product on the performance of the silicon rubber, but also the metal oxide can react with the fatty acid to generate a fatty acid salt crosslinking activator, and the fatty acid salt can obviously improve the vulcanization efficiency and the processing performance of the silicon rubber and the crosslinking density of vulcanized rubber, and particularly greatly improve the heat resistance of the silicon rubber.
(2) The invention adopts a reaction blending modification method to carry out epoxidation modification on the silicon rubber, and has the obvious advantages of no solvent, high efficiency, simple process, low cost and the like compared with the traditional solution modification method.
(3) The invention introduces the phosphorus-containing flame retardant intermediate into the molecular chain of the silicone rubber by adopting a reaction blending modification method, provides a new method for preparing intrinsic flame-retardant silicone rubber, and has no related report at present. The method has very obvious beneficial effect on improving the flame retardance of the silicon rubber.
(4) The phosphorus-containing intrinsic flame-retardant silicone rubber has good flame retardance, can reach the UL94-V0 combustion grade, has the properties of high efficiency, no halogen, no smoke, no toxicity, good elastic restoring force and the like, is suitable for being used as a protective material for complex electrical systems such as new energy automobiles, electric power and the like, is particularly suitable for the field of electrical protection with harsh requirements, and provides high-reliability safety protection for electrical components.
Drawings
FIG. 1 is a photograph showing a burning process of the phosphorus-containing intrinsic flame retardant silicone rubber in example 1 of the present invention.
FIG. 2 is a vulcanization curve of different silicone rubber compounds according to example 1 of the invention.
FIG. 3 is a photograph showing a burning process of the phosphorus-containing intrinsic flame retardant silicone rubber in example 2 of the present invention.
FIG. 4 is a vulcanization curve of different silicone rubber compounds of example 2 of the present invention.
Detailed Description
The present invention is described in further detail below with reference to examples, which are intended to facilitate the understanding of the present invention without limiting it in any way.
Example 1:
the preparation method of the phosphorus-containing intrinsic flame-retardant silicone rubber comprises the following steps:
step (1) hardness of 30A and molecular weight of 50X 104Adding raw methyl vinyl silicone rubber with g/mol and 1.2 percent of vinyl molar content into a vacuum kneader, plasticating under vacuum condition at the plasticating temperature of 150 ℃, the plasticating time of 40min and the rotor speed of 100rpm to prepare the methyl ethyleneSilicon rubber plasticated rubber.
And (2) sequentially adding 5.2 parts of m-chloroperoxybenzoic acid and 5.5 parts of zinc oxide into the vacuum kneader in the step (1), mixing with 100 parts of methyl vinyl silicone rubber plasticated rubber under a vacuum condition, wherein the mixing temperature is 40 ℃, the mixing time is 60min, and the rotor speed is 65rpm, so that vinyl on a molecular chain of the methyl vinyl silicone rubber reacts with peroxy groups on the m-chloroperoxybenzoic acid to obtain the epoxidized methyl vinyl silicone rubber.
And (3) adding 16 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into the vacuum kneader in the step (2), mixing with the epoxidized methyl vinyl silicone rubber under vacuum conditions, wherein the mixing temperature is 100 ℃, the mixing time is 120min, the rotor speed is 60rpm, and the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide reacts with the epoxidized methyl vinyl silicone rubber in the mixing process to obtain the primary phosphorus-containing intrinsic flame-retardant methyl vinyl silicone rubber.
And (4) adding the primary phosphorus-containing intrinsic flame-retardant silicone rubber into a rubber filter, filtering by using a 500-mesh filter screen to remove impurities, wherein the temperature of a charging barrel is 80 ℃, and thus obtaining the phosphorus-containing intrinsic flame-retardant methyl vinyl silicone rubber.
The combustion test of the prepared phosphorus-containing intrinsic flame-retardant silicone rubber is shown in figure 1, which shows that the phosphorus-containing intrinsic flame-retardant silicone rubber has a flame-retardant effect and reaches the UL94-V0 combustion grade.
In order to investigate the vulcanization characteristics, mechanics, flame retardance and other physicochemical properties of the intrinsic phosphorus-containing flame-retardant methyl vinyl silicone rubber prepared in the above manner, a formulation design is carried out according to the proportion of each component in table 1 by using methyl vinyl silicone rubber which is not modified at all as a reference, a mixed rubber sample No. 1 and a sample No. 2 which are uniformly mixed in the formulation are subjected to compression molding at 170 ℃ for 10 minutes, and secondary vulcanization is carried out at 200 ℃ for 4 hours to obtain a silicon rubber vulcanized rubber sample No. 1 and a sample No. 2.
TABLE 1 formulation of the components of the silicone rubber
FIG. 2 is a graph showing the vulcanization curves of the silicone rubber compound No. 1 sample and the silicone rubber compound No. 2 sample. As can be seen from fig. 2, the phosphorus-containing intrinsic flame retardant methylvinylsiloxane rubber exhibits higher vulcanization efficiency and crosslinking density compared to the unmodified methylvinylsiloxane rubber.
Table 2 shows various physicochemical properties of the silicone rubber vulcanizate 1# sample and the silicone rubber vulcanizate 2# sample. As can be seen from Table 2, compared with unmodified methyl vinyl silicone rubber, the intrinsic phosphorus-containing flame-retardant methyl vinyl silicone rubber not only has better mechanical properties and heat resistance, but also has very excellent flame retardant property.
TABLE 2 various physico-chemical properties of the silicone rubber vulcanizates
Example 2:
the preparation method of the phosphorus-containing intrinsic flame-retardant silicone rubber comprises the following steps:
step (1) hardness of 40A and molecular weight of 62 x 104Adding raw methyl vinyl phenyl silicone rubber with g/mol and 0.9 percent of vinyl molar content into a vacuum kneader, and plasticating under the vacuum condition, wherein the plasticating temperature is 160 ℃, the plasticating time is 30min, and the rotor speed is 120rpm to prepare the methyl vinyl phenyl silicone rubber plasticated rubber.
And (2) sequentially adding 4 parts of peroxybenzoic acid and 5 parts of zinc oxide into the vacuum kneader in the step (1), and mixing with 100 parts of methylvinylphenyl silicone rubber plasticated rubber under a vacuum condition, wherein the mixing temperature is 55 ℃, the mixing time is 50min, and the rotor speed is 40rpm, so that vinyl on a molecular chain of the methylvinylphenyl silicone rubber reacts with peroxy groups on the peroxybenzoic acid, and the epoxidized methylvinylphenyl silicone rubber is obtained.
And (3) adding 22 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1.5 parts of triphenylphosphine into the vacuum kneader in the step (2), mixing with the epoxidized silicone rubber under the vacuum condition, wherein the mixing temperature is 80 ℃, the mixing time is 160min, the rotor speed is 55rpm, and the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the epoxidized methylvinylphenyl silicone rubber react in the mixing process to obtain the primary phosphorus-containing intrinsic flame-retardant methylvinylphenyl silicone rubber.
And (4) adding the primary phosphorus-containing intrinsic flame-retardant silicone rubber into a rubber filter, filtering by using a 300-mesh filter screen to remove impurities, wherein the temperature of a charging barrel is 65 ℃, and thus obtaining the phosphorus-containing intrinsic flame-retardant methyl vinyl phenyl silicone rubber.
The combustion test of the prepared phosphorus-containing intrinsic flame-retardant silicone rubber is shown in figure 3, which shows that the phosphorus-containing intrinsic flame-retardant silicone rubber has a flame-retardant effect and reaches the UL94-V0 combustion grade.
In order to investigate the vulcanization characteristics, mechanics, flame retardance and other physicochemical properties of the intrinsic phosphorus-containing flame-retardant silicon methyl vinyl phenyl silicone rubber prepared in the above way, methyl vinyl phenyl silicone rubber which is not modified at all is adopted as a reference, formula design is carried out according to the proportion of each component in table 3, a mixed rubber sample No. 1 and a sample No. 2 are molded for 12 minutes at 180 ℃ after the formula is uniformly mixed, and secondary vulcanization is carried out for 3 hours at 210 ℃ to obtain a silicon rubber vulcanized rubber sample No. 1 and a sample No. 2.
TABLE 3 formulation of the components of the silicone rubber
FIG. 4 is a graph showing the vulcanization curves of the silicone rubber compound No. 1 sample and the silicone rubber compound No. 2 sample. As can be seen from fig. 4, the phosphorus-containing intrinsic flame retardant methylvinylphenyl silicone rubber exhibited higher vulcanization efficiency and crosslink density compared to the unmodified methylvinylphenyl silicone rubber.
Table 4 shows various physicochemical properties of the silicone rubber vulcanizate 1# sample and the silicone rubber vulcanizate 2# sample. As can be seen from Table 4, the intrinsic phosphorus-containing flame retardant methylvinylphenyl silicone rubber not only has good mechanical properties and heat resistance, but also has very excellent flame retardant properties, compared with unmodified methylvinylphenyl silicone rubber.
TABLE 4 various physico-chemical properties of the silicone rubber vulcanizates
| Performance parameter | Unit of | 1# | 2# |
| Specific gravity of | — | 1.28 | 1.26 |
| Hardness of | Type A of Shao's disease | 62A | 58A |
| Tensile strength | MPa | 7.9 | 7.5 |
| Elongation at break | ％ | 343 | 321 |
| Tear strength | kN/m | 18.2 | 16.3 |
| Compression set (177 ℃, 24h) | ％ | 19.3 | 18.7 |
| Flame retardant Properties (UL 94 rating) | — | V-0 | HB |
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for improving the vulcanization efficiency, the crosslinking density and the flame retardant property of silicon rubber without solvent is characterized in that: the method comprises the following steps:
adding raw silicone rubber into a vacuum kneader, and plasticating under a vacuum condition to prepare silicone rubber plasticated rubber; the raw silicon rubber is heat-vulcanized silicon rubber containing vinyl, and the molar content of the vinyl in the raw silicon rubber is 0.5-2.0%;
step (2) sequentially adding an organic peroxy acid epoxidation reagent and a metal oxide into the vacuum kneader in the step (1), and mixing the mixture with the silicone rubber plasticated rubber under a vacuum condition to enable vinyl of a silicone rubber molecular chain to react with a peroxy group of the epoxidation reagent to form an epoxy group, so as to obtain epoxidized silicone rubber;
adding the phosphorus-containing flame retardant intermediate into the vacuum kneader in the step (2), mixing with the epoxidized silicone rubber under a vacuum condition, and reacting the phosphorus-containing flame retardant intermediate with the epoxidized silicone rubber in the mixing process to obtain primary phosphorus-containing intrinsic flame retardant silicone rubber; the phosphorus-containing flame retardant intermediate is one or more of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof;
and (4) adding the primary phosphorus-containing intrinsic flame-retardant silicone rubber into a rubber filter for filtering to remove impurities, thereby obtaining the phosphorus-containing intrinsic flame-retardant silicone rubber.
2. The method of claim 1, further comprising: the raw silicon rubber comprises one or more of methyl vinyl silicon rubber, methyl vinyl phenyl silicon rubber and methyl vinyl trifluoropropyl silicon rubber.
3. The method of claim 1, further comprising: the epoxidation reagent comprises one or more of peroxyformic acid, peroxyacetic acid, peroxybenzoic acid, m-chloroperoxybenzoic acid and tert-butyl hydroperoxide.
4. The method of claim 1, further comprising: the metal oxide comprises one or more of zinc oxide, magnesium oxide and calcium oxide.
5. The method of claim 1, further comprising: in the step (2), the mass parts of the epoxidation reagent and the metal oxide are respectively 2-12 parts and 3-15 parts, based on 100 parts of the silicone rubber plasticated rubber.
6. The method of claim 1, further comprising: in the step (3), the amount of the phosphorus-containing flame retardant intermediate is 5-35 parts by mass based on 100 parts by mass of the epoxidized silicone rubber.
7. The method of any of claims 1 to 6, wherein: in the step (3), triphenylphosphine serving as a catalyst is added.
8. The method of claim 7, further comprising: the addition mass of the triphenylphosphine is 0.5-10% of the mass of the phosphorus-containing flame retardant intermediate.
9. The method of any of claims 1 to 6, wherein: the flame retardance of the intrinsic flame-retardant silicone rubber containing phosphorus reaches UL94-V0 combustion rating.
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