Flame-retardant polytriecyclopentadiene PTCPD material and preparation method thereof
阅读说明：本技术 阻燃性聚三环戊二烯ptcpd材料及其制备方法 (Flame-retardant polytriecyclopentadiene PTCPD material and preparation method thereof ) 是由 刘畅 于 2021-02-10 设计创作，主要内容包括：本发明公开了一种阻燃性聚三环戊二烯PTCPD材料及其制备方法,所述材料包括以下组分：三环戊二烯TCPD,催化剂,阻燃剂；其中,所述三环戊二烯TCPD的重量百分比为51％～90％,所述阻燃剂的重量为所述三环戊二烯TCPD的重量的10％～40％。由于TCPD的分子量大,刚性大,所制得的PTCPD高分子材料的刚性远大于现有的聚双环戊二烯高分子材料的刚性,阻燃剂的添加使得材料具有很好的阻燃性。同时PTCPD高分子材料还具有耐酸、耐碱、耐海水腐蚀、耐疲劳等优异特性,应用范围广泛。(The invention discloses a flame-retardant polytriecyclopentadiene PTCPD material and a preparation method thereof, wherein the material comprises the following components: tricyclopentadiene TCPD, a catalyst and a flame retardant; wherein the weight percentage of the tricyclopentadiene TCPD is 51-90%, and the weight of the flame retardant is 10-40% of the weight of the tricyclopentadiene TCPD. Because TCPD has large molecular weight and high rigidity, the rigidity of the prepared PTCPD high polymer material is far greater than that of the existing polydicyclopentadiene high polymer material, and the material has good flame retardance due to the addition of the flame retardant. Meanwhile, the PTCPD high polymer material also has the excellent characteristics of acid resistance, alkali resistance, seawater corrosion resistance, fatigue resistance and the like, and has a wide application range.)
1. A flame retardant polytrieopentadiene PTCPD material, characterized in that the material comprises the following components:
tricyclopentadiene TCPD;
a catalyst;
a flame retardant;
wherein, the weight percentage of the tricyclopentadiene TCPD is 51-90%.
2. The flame retardant polytrieopentadiene PTCPD material of claim 1, wherein the composition of the material further comprises one or more of cyclopentadiene, dicyclopentadiene, tetracyclopentadiene, and pentacyclopentadiene.
3. The flame retardant polytrieopentadiene PTCPD material according to claim 1, wherein the flame retardant is one or more of magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, octabromoether, triphenyl phosphate, hexabromocyclododecane, zinc borate, decabromodiphenylethane, coated red phosphorus, chlorinated paraffin, chlorosulfonylated polyethylene, chlorinated polypropylene, chlorinated polyethylene, and halogenated norbornene.
4. The flame retardant polytrieopentadiene PTCPD material of claim 1, wherein the weight of the flame retardant is 10% to 40% of the weight of the tricyclopentadiene TCPD.
5. The flame retardant polytrieopentadiene PTCPD material of claim 1, wherein the catalyst comprises a procatalyst and a cocatalyst.
6. The flame retardant polytrieopentadiene PTCPD material of claim 5, wherein the catalyst further comprises a modifier selected from the group consisting of oxygen, alcohols, phenols, BF3One or more of them.
7. The flame retardant polytrieopentadiene PTCPD material of claim 1, wherein the weight of the catalyst is from 0.01% to 1% of the weight of the tricyclopentadiene TCPD.
8. A preparation method of a flame-retardant polytriecyclopentadiene PTCPD material is characterized by comprising the following steps:
a, B two components are prepared from raw materials, wherein the component A comprises tricyclopentadiene TCPD, a cocatalyst and a flame retardant, and the component B comprises tricyclopentadiene TCPD and a main catalyst;
proportionally mixing the A, B two components and injecting the mixture into a cavity of a closed mold; heating, polymerizing the mixture, and crosslinking, curing and molding;
and opening the mould, and demoulding to obtain the flame-retardant polytriecyclopentadiene PTCPD material product.
9. The method for preparing a flame retardant polytrieopentadiene PTCPD material according to claim 8, wherein the weight percentage of the tricyclopentadiene TCPD in the raw material is 51-90%, and the weight of the flame retardant is 10-40% of the weight of the tricyclopentadiene TCPD.
10. The method for preparing the flame retardant polytrieopentadiene PTCPD material according to claim 8, wherein the main catalyst is one or more of tungsten catalyst, molybdenum catalyst, ruthenium catalyst, titanium catalyst and rhenium catalyst;
the cocatalyst is one or more of metal organic compounds of aluminum, magnesium, tin, zinc and silicon.
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a flame-retardant polytriecyclopentadiene PTCPD material and a preparation method thereof.
Background
The polydicyclopentadiene PDCPD polymer material is homopolymer or copolymer of dicyclopentadiene DCPD, and is a cross-linked three-dimensional network structure engineering plastic. The polydicyclopentadiene PDCPD is a material with the characteristics of good heat resistance, creep resistance, dimensional stability, shape memory, corrosion resistance, light weight and the like, and can be used for manufacturing various high-performance, high-added-value and high-grade fine products. Such as: automobile bumpers, guard plates, side plates, buffer plates, instrument panels, mud guards, engine covers, body shells and the like in the transportation industry; housings for large-sized electrical devices such as motors and air conditioners in electrical devices; parts of snowmobiles, surfboards, golf carts, etc. in sports equipment, agricultural machinery, civil engineering and construction materials, etc.
However, in the process of implementing the technical solution of the invention in the embodiments of the present application, the inventors of the present application find that the above-mentioned technology has at least the following technical problems:
although polydicyclopentadiene PDCPD has good comprehensive performance, the strength of the polydicyclopentadiene PDCPD cannot meet the higher requirements in certain specific engineering fields. The bending modulus of the polydicyclopentadiene PDCPD high polymer material is about 1790-2070 MPa, and the material rigidity of the polydicyclopentadiene PDCPD can not meet the requirement on the working condition with higher requirement on the bending modulus.
In addition, polydicyclopentadiene PDCPD is flammable, and can be burned if the temperature is higher than the ignition point when meeting a fire source, so that how to retard the fire is always a difficult problem which is solved by the technical personnel in the field.
Disclosure of Invention
The embodiment of the application provides a flame-retardant polytriepentadiene PTCPD material, solves the technical problems that the material rigidity of polydicyclopentadiene PDCPD in the prior art is insufficient and flammable, has high strength and good flame retardance, and also has excellent characteristics of acid resistance, alkali resistance, salt water corrosion resistance, halogen gas corrosion resistance, fatigue resistance and the like, and has a wide application range.
The embodiment of the application provides a flame-retardant polytriecyclopentadiene PTCPD material, which is characterized by comprising the following components:
tricyclopentadiene TCPD;
a catalyst;
a flame retardant;
wherein, the weight percentage of the tricyclopentadiene TCPD is 51-90%.
Preferably, the material further comprises one or more of cyclopentadiene, dicyclopentadiene, tetracyclopentadiene and pentacyclopentadiene.
Preferably, the flame retardant is one or more of magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, octabromoether, triphenyl phosphate, hexabromocyclododecane, zinc borate, decabromodiphenylethane, coated red phosphorus, chlorinated paraffin, chlorosulfonylated polyethylene, chlorinated polypropylene, chlorinated polyethylene and halogenated norbornene.
Preferably, the weight of the flame retardant is 10-40% of the weight of the tricyclopentadiene TCPD.
Preferably, the catalyst comprises a main catalyst and a cocatalyst;
the main catalyst is one or more of tungsten catalyst, molybdenum catalyst, ruthenium catalyst, titanium catalyst and rhenium catalyst;
the cocatalyst is one or more of metal organic compounds of aluminum, magnesium, tin, zinc and silicon.
Preferably, the catalyst further comprises a regulator, wherein the regulator is oxygen, alcohol, phenol or BF3One or more of them.
Preferably, the weight of the catalyst is 0.01-1% of the weight of the tricyclopentadiene TCPD.
The embodiment of the application also provides a preparation method of the flame-retardant polytriecyclopentadiene PTCPD material, which is characterized by comprising the following steps:
a, B two components are prepared from raw materials, wherein the component A comprises tricyclopentadiene TCPD, a cocatalyst and a flame retardant, and the component B comprises tricyclopentadiene TCPD and a main catalyst;
proportionally mixing the A, B two components and injecting the mixture into a cavity of a closed mold; heating, polymerizing the mixture, and crosslinking, curing and molding;
and opening the mould, and demoulding to obtain the flame-retardant polytriecyclopentadiene PTCPD material product.
Preferably, the weight percentage of the tricyclopentadiene TCPD in the raw material is 51-90%, and the weight of the flame retardant is 10-40% of the weight of the tricyclopentadiene TCPD.
Preferably, the component A also comprises one or more of cyclopentadiene, dicyclopentadiene, tetracyclopentadiene and pentacyclopentadiene.
Preferably, the main catalyst is one or more of a tungsten catalyst, a molybdenum catalyst, a ruthenium catalyst, a titanium catalyst and a rhenium catalyst;
the cocatalyst is one or more of metal organic compounds of aluminum, magnesium, tin, zinc and silicon.
Further, the tungsten catalyst comprises one or more of a tungsten simple substance, tungsten oxide, tungsten halide, tungsten hydroxyl compound and heteropolytungstic acid;
further, the molybdenum catalyst comprises one or more of molybdenum simple substance, molybdenum oxide, molybdenum halide, molybdenum hydroxyl compound, phosphomolybdic acid and ammonium molybdate;
further, the ruthenium catalyst is one or more of metal ruthenium, ruthenium oxide, ruthenium halide and ruthenium hydroxyl compound;
further, the titanium catalyst is one or more of metal titanium, titanium oxide, titanium halide and titanium hydroxyl compound;
further, the rhenium catalyst is one or more of metal rhenium, rhenium oxide, rhenium halide and rhenium hydroxyl compound.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
1. the application provides a novel flame-retardant polytriepentadiene PTCPD material, the material component contains a high proportion of tricyclopentadiene TCPD, and because the molecular weight of the tricyclopentadiene TCPD is large and the rigidity is large, the rigidity of the prepared flame-retardant polytriepentadiene PTCPD material is far greater than that of the existing polydicyclopentadiene PDCPD high molecular material, and meanwhile, the material has good flame retardance due to the addition of a flame retardant.
2. The flame-retardant polytriecyclopentadiene PTCPD material provided by the application also has excellent characteristics of acid resistance, alkali resistance, salt water corrosion resistance, halogen gas corrosion resistance, fatigue resistance and the like, and is wide in application range.
Detailed Description
The embodiment of the application provides a flame-retardant polytrieopentadiene PTCPD material, and solves the technical problems that the material of polydicyclopentadiene PDCPD in the prior art is insufficient in rigidity and inflammable.
In order to solve the above problems, the technical solution in the embodiment of the present application has the following general idea:
a novel flame-retardant polytrieopentadiene PTCPD material is designed, and the material mainly comprises the following components:
the tricyclopentadiene TCPD material accounts for 51 to 90 percent by weight;
a catalyst;
and (3) a flame retardant.
The flame-retardant polytrieopentadiene PTCPD material also can contain one or more of cyclopentadiene, dicyclopentadiene, tetracyclopentadiene, pentacyclopentadiene and the like.
The flame retardant is one or more of magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, octabromoether, triphenyl phosphate, hexabromocyclododecane, zinc borate, decabromodiphenylethane, coated red phosphorus, chlorinated paraffin, chlorosulfonated polyethylene, chlorinated polypropylene, chlorinated polyethylene and halogenated norbornene.
The weight of the flame retardant is 10-40% of the weight of the tricyclopentadiene TCPD.
The catalyst comprises one or more of tungsten catalyst, molybdenum catalyst, ruthenium catalyst, titanium catalyst and rhenium catalyst.
The catalyst also comprises one or more of metal organic compounds of aluminum, magnesium, tin, zinc and silicon. Such as triethylaluminum, tributylaluminum, diethylaluminum monochloride, triisobutylaluminum, etc.
The catalyst also contains oxygen, alcohol, phenol and BF3One or more of them.
The tungsten catalyst comprises one or more of tungsten simple substance, tungsten oxide, tungsten halide (such as tungsten sulfide and tungsten chloride), tungsten hydroxyl compound and heteropolytungstic acid;
the molybdenum catalyst comprises one or more of molybdenum simple substance, molybdenum oxide, molybdenum halide, molybdenum hydroxyl compound, phosphomolybdic acid and ammonium molybdate;
the ruthenium catalyst is one or more of ruthenium metal, ruthenium oxide, ruthenium halide and ruthenium hydroxyl compound; such as Grubbs 'I, Grubbs' II ruthenium catalysts.
The titanium catalyst is one or more of metal titanium, titanium oxide, titanium halide and titanium hydroxyl compound;
the rhenium catalyst is one or more of metal rhenium, rhenium oxide, rhenium halide and rhenium hydroxyl compound.
The weight of the catalyst is 0.01-1% of the total weight of the tricyclopentadiene TCPD.
Because the molecular weight of the tricyclopentadiene TCPD is large, the rigidity of the tricyclopentadiene TCPD is large, and the rigidity of the prepared flame-retardant polytriepentadiene PTCPD material is far greater than that of the existing polydicyclopentadiene PDCPD high molecular material. Meanwhile, the material has good flame retardance due to the addition of the flame retardant.
In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments.
Example one
The embodiment of the application provides a flame-retardant polytriecyclopentadiene PTCPD material which comprises the following components:
dicyclopentadiene, 51 percent by weight;
dicyclopentadiene, 28.09 percent by weight;
WCl60.127 percent by weight;
AlEt2cl, 0.383 percent by weight;
hexaphenoxycyclotriphosphazene, 20.4% by weight;
in this example, the preparation process of the flame retardant polytriecyclopentadiene PTCPD material product is as follows:
step S1: the raw materials are prepared into A, B two components, wherein the component A comprises tricyclopentadiene TCPD, dicyclopentadiene and AlEt2Cl and hexaphenoxycyclotriphosphazene, wherein the component B is tricyclopentadiene TCPD and WCl6；
Step S2: a, B mixing the two components and injecting the mixture into the cavity of a closed mold; heating to 50 ℃, and quickly polymerizing the mixture, and crosslinking, curing and molding;
step S3: and opening the mold, and demolding to obtain the flame-retardant polytriecyclopentadiene PTCPD material product.
The flexural modulus of the flame-retardant polytrieyclopentadiene PTCPD material product prepared by the embodiment is 3184 MPa.
The product sample is subjected to a combustion experiment according to ANSI/UL-94 standard, and the result shows that the flame retardant value of the product sample is V-0, so that the flame retardant polytriecyclopentadiene PTCPD material product prepared in the embodiment has good flame retardant property.
Example two
The embodiment of the application provides a flame-retardant polytriecyclopentadiene PTCPD material which comprises the following components:
tricyclopentadiene TCPD, 70% by weight;
dicyclopentadiene, 7% by weight;
1.65 percent of tetracyclopentadiene;
ReCls, 0.09% by weight;
(CH3)4sn, 0.26 percent by weight;
chlorinated paraffin, 21% by weight.
In this example, the preparation process of the flame retardant polytriecyclopentadiene PTCPD material product is as follows:
step S1: the raw materials are prepared into A, B two components, wherein the component A comprises tricyclopentadiene TCPD, dicyclopentadiene, tetracyclopentadiene, (CH)3)4Sn and chlorinated paraffin, wherein the component B comprises tricyclopentadiene TCPD and molybdenum ReCls;
step S2: a, B mixing the two components and injecting the mixture into the cavity of a closed mold; heating to 72 ℃, and quickly polymerizing the mixture, and crosslinking, curing and molding;
step S3: and opening the mold, and demolding to obtain the flame-retardant polytriepentadiene PTCPD material.
The flexural modulus of the flame-retardant polytrieyclopentadiene PTCPD material product prepared by the embodiment is 3210 MPa.
The product sample is made into a sheet for a combustion experiment, the sample is horizontally suspended, a blast burner is used for ignition for 30s, then the blast burner is moved away, and the combustion flame of the sample is extinguished at a position 16-60 mm away from the ignition point. When the chlorinated paraffin flame retardant is not added, the test sample is burnt out at the burning speed of 34mm/min under the same burning experiment.
EXAMPLE III
The embodiment of the application provides a flame-retardant polytriecyclopentadiene PTCPD material which comprises the following components:
80% by weight of tricyclopentadiene TCPD;
3.6 percent of dicyclopentadiene;
CpTiCl20.1 percent by weight;
CH3MgI, 0.3 percent by weight;
16 percent of aluminum hydroxide.
In this example, the preparation process of the flame retardant polytriecyclopentadiene PTCPD material product is as follows:
step S1: the raw materials are prepared into A, B two components, wherein the component A comprises tricyclopentadiene TCPD, dicyclopentadiene, pentacyclopentadiene and CH3MgI, aluminium hydroxide, B component of tricyclopentadiene TCPD and CpTiCl2；
Step S2: a, B mixing the two components and injecting the mixture into the cavity of a closed mold; heating to 65 ℃, and quickly polymerizing the mixture, and crosslinking, curing and molding;
step S3: and opening the mold, and demolding to obtain the flame-retardant polytriepentadiene PTCPD material.
The flexural modulus of the flame-retardant polytrieyclopentadiene PTCPD material product prepared by the embodiment is 3304 MPa.
The product sample is subjected to a combustion experiment according to the ANSI/UL-94 standard, and the result shows that the flame-retardant polytriecyclopentadiene PTCPD material product prepared by the embodiment has good flame retardance.
Example four
The embodiment of the application provides a flame-retardant polytriecyclopentadiene PTCPD material which comprises the following components:
90% by weight of tricyclopentadiene TCPD;
grubbs' ruthenium I catalyst, 1% by weight;
trichloronorbornene, 9% by weight.
In this example, the preparation process of the flame retardant polytriecyclopentadiene PTCPD material product is as follows:
step S1: preparing A, B two components from raw materials, wherein the component A is tricyclopentadiene TCPD, and the component B is Grubbs' I ruthenium catalyst solution;
step S2: a, B mixing the two components and injecting the mixture into the cavity of a closed mold; heating to 78 deg.c to polymerize the mixture and crosslink and cure;
step S3: and opening the mold, and demolding to obtain the flame-retardant polytriecyclopentadiene PTCPD material product.
The flexural modulus of the flame-retardant polytrieyclopentadiene PTCPD material product prepared by the embodiment is 3410 MPa.
The burning test was carried out on the product sample in accordance with JIS K-6911, and the flame burning distance was 7 mm. Under the same working condition, the flame combustion distance of the product without the flame retardant is 125 mm. The flame retardance of the flame-retardant polytriecyclopentadiene PTCPD material product added with the flame retardant is obviously improved.
While the foregoing is directed to the preferred embodiment of the present application, and not to the limiting thereof in any way and any way, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. Those skilled in the art can make various changes, modifications and equivalent arrangements to those skilled in the art without departing from the spirit and scope of the present application; moreover, any equivalent alterations, modifications and variations of the above-described embodiments according to the spirit and techniques of this application are intended to be within the scope of the claims of this application.