CN117866443A - Flame-retardant silicone rubber material and preparation method and application thereof - Google Patents
Flame-retardant silicone rubber material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117866443A CN117866443A CN202311849497.XA CN202311849497A CN117866443A CN 117866443 A CN117866443 A CN 117866443A CN 202311849497 A CN202311849497 A CN 202311849497A CN 117866443 A CN117866443 A CN 117866443A
- Authority
- CN
- China
- Prior art keywords
- silicone rubber
- flame retardant
- rubber material
- parts
- flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 135
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 120
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000003063 flame retardant Substances 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- HKKBJRUSFKTHSU-UHFFFAOYSA-N n-[chloro(diethylamino)phosphoryl]-n-ethylethanamine Chemical compound CCN(CC)P(Cl)(=O)N(CC)CC HKKBJRUSFKTHSU-UHFFFAOYSA-N 0.000 claims abstract description 34
- -1 3-hydroxyphenylboronic acid methyl iminodiacetic acid ester Chemical class 0.000 claims abstract description 31
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims abstract description 26
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000002195 synergetic effect Effects 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 46
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical group C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 38
- 238000004073 vulcanization Methods 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 229920001971 elastomer Polymers 0.000 claims description 23
- 239000006229 carbon black Substances 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 6
- QWHBAQJRYFNJFT-UHFFFAOYSA-N 2-[(2-methoxy-2-oxoethyl)azaniumyl]acetate Chemical compound COC(=O)CNCC(O)=O QWHBAQJRYFNJFT-UHFFFAOYSA-N 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 239000000779 smoke Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 2
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 16
- 229920002554 vinyl polymer Polymers 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a flame-retardant silicone rubber material, a preparation method and application thereof, and relates to the technical field of polymer material processing. The flame-retardant silicone rubber material is prepared from silicone rubber, filler, a phosphorus-boron synergistic flame retardant and a vulcanizing agent, wherein the phosphorus-boron synergistic flame retardant is prepared by reacting 3-hydroxyphenylboronic acid methyl iminodiacetic acid ester with bis (diethylamino) phosphoryl chloride and vinyl triacetoxy silane. The 3-hydroxyphenylboronic acid methyl iminodiacetic acid ester has higher phenolic hydroxyl reaction activity in a molecular chain, and reacts with bis (diethylamino) phosphoryl chloride and vinyl triacetoxy silane to generate the phosphorus-boron synergistic flame retardant BPDM, the flame retardant does not contain halogen groups, has better compatibility with silicone rubber, improves the mechanical property of the silicone rubber, can improve the char formation amount of the silicone rubber in the combustion process, and better inhibits the generation of smoke, thereby achieving excellent flame retardant effect.
Description
Technical Field
The invention relates to the technical field of polymer material processing, in particular to a flame-retardant silicone rubber material, and a preparation method and application thereof.
Background
With the continuous increase of urban population density and the continuous development of the power industry, the national life quality is continuously improved, and simultaneously, higher requirements are put on the power transmission capacity of a power cable transmission system, so that the cable accessory is used as a necessary device for connecting a cable body and electric energy transmission, and not only can the voltage class of 220KV and below be met, but also the voltage class of higher level can be met.
The development of the high-voltage cable accessory is a complex process, and the materials applied to the accessory at present mainly comprise ethylene propylene diene monomer rubber and silicone rubber. Because of the high hardness of the ethylene propylene diene monomer, the ethylene propylene diene monomer has certain difficulty in the process of installing accessories. The silicone rubber has excellent high and low temperature resistance, ozone resistance, tearing resistance, weather resistance and good insulativity, can meet the requirements of the high-voltage cable on the safety and reliability of accessories to a great extent, and is easy to crosslink and solidify without melting when encountering high temperature or short circuit. In view of the installation and maintenance convenience, operation safety and other aspects of the high-voltage cable accessories, the silicone rubber is increasingly applied to the high-voltage cable accessories, such as 10-35KV wire mesh separable shielding type cable accessories, cold shrinkage type accessories, prefabricated stress cones, outer insulating sleeves and the like.
Because of the general fire resistance of the silicone rubber cable accessory material itself, and the serious dripping phenomenon, the silicone rubber cable accessory material may ignite other surrounding materials while burning, thereby limiting further application of the silicone rubber cable accessory material in both high thermal stability and remarkable flame retardance. Therefore, how to improve the flame retardancy of high voltage cable accessories remains one of the problems that needs to be solved at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the flame-retardant silicone rubber material, and the preparation method and application thereof, which can effectively improve the flame retardant property of the flame-retardant silicone rubber material and simultaneously maintain good physical and mechanical properties, so that the flame-retardant silicone rubber material can be effectively applied to the preparation of high-voltage cable accessory materials.
In order to achieve the above object, the technical scheme of the present invention is realized by the following technical scheme:
the flame-retardant silicone rubber material is prepared from the following raw materials in parts by weight: 100-110 parts of silicon rubber, 20-40 parts of filler, 10-45 parts of phosphorus-boron synergistic flame retardant and 2-7 parts of vulcanizing agent; wherein the phosphorus-boron synergistic flame retardant is prepared from 3-hydroxyphenylborate methyl iminodiacetate, bis (diethylamino) phosphoryl chloride and vinyl triacetoxy silane according to the mass ratio of 1.1-3.5: 1: and (3) carrying out a compounding reaction at 0.2-0.6.
Preferably, the silicone rubber is methyl vinyl silicone rubber; the filler is white carbon black; the vulcanizing agent is two to five.
The preparation method of the flame-retardant silicone rubber material comprises the following steps:
(1) Dropwise adding dimethyl formamide into 3-hydroxyphenylboronic acid methyl iminodiacetic acid ester to stir and dissolve, so as to obtain a dissolving solution for standby;
(2) Adding bis (diethylamino) phosphoryl chloride into the solution, carrying out suction filtration after mixing reaction, washing, and drying to obtain a dried product for later use;
(3) Adding the dried product into vinyl triacetoxy silane, and stirring and dispersing to obtain a phosphorus-boron synergistic flame retardant;
(4) Placing the silicon rubber on an open mill, starting plasticating, adding a filler and a phosphorus-boron synergistic flame retardant for mixing after plasticating is finished, and obtaining a mixed rubber;
(5) And adding a vulcanizing agent into the rubber compound, mixing, blanking, and vulcanizing the rubber sheet to obtain the flame-retardant silicone rubber material.
Preferably, the temperature of stirring and dissolving in the step (1) is 30 ℃, and the stirring time is 15-20min.
Preferably, the temperature of the mixing reaction in the step (2) is 40-55 ℃, the reaction time is 4-7h, and the drying mode is drying in an oven at 105 ℃ for 2h.
Preferably, the stirring and dispersing rotational speed in the step (3) is 1000-1500 r/min, and the stirring time is 10-15s.
Preferably, in the step (4), the mixing temperature of the open mill is set to be 30-40 ℃, and the mixing roll gap is adjusted to be 4-5 mm.
Preferably, the filler and the phosphorus-boron synergistic flame retardant in the step (4) are added in 3-6 times, and the interval between each addition is 2-8 min.
Preferably, in the step (5), the roll gap is adjusted to 2-3 mm, the mixing and the sheet discharging are carried out in a triangle bag mode, the vulcanization temperature is 170-180 ℃, the vulcanization pressure is 10-15MPa, and the vulcanization time is 3-10min.
And the flame retardant silicone rubber material obtained above can be used for preparing cable accessory materials.
The invention provides a flame-retardant silicone rubber material, a preparation method and application thereof, and has the advantages compared with the prior art that:
(1) The 3-hydroxyphenylboronic acid methyl iminodiacetic acid ester has higher reactivity of phenolic hydroxyl groups, can react with bis (diethylamino) phosphoryl chloride under certain conditions, and generates a phosphorus-boron integrated synergistic BPDM flame retardant after the reaction product of the 3-hydroxyphenylboronic acid methyl iminodiacetic acid ester and vinyl triacetoxy silane are combined, wherein the flame retardant has extremely high flame retardant efficiency in silicon rubber; and BPDM flame retardant can be dehydrated into a ring after being heated, a boron-oxygen six-membered ring network structure is easy to form, the structure can form more carbon layers containing B-O-C bonds after further combustion, and the formation of the carbide can prevent heat transfer and prevent the silicon rubber from being further oxidized;
(2) The BPDM flame retardant containing phosphorus atoms in the invention can generate phosphoric acid in the heating process, and the phosphoric acid can be condensed with a C-O bond to form polyphosphoric acid crosslinking, and can also form stable BPO with boron element at high temperature 4 The compact protective carbon layer formed by the catalysis of the two can reduce the generation of gas phase products and carbonyl compounds to the maximum extent;
(3) The BPDM prepared by the invention is used as a boron, phosphorus and silicon-containing low molecular organic compound, can act with Si-OH groups on the surface of white carbon black, improves the affinity between silicon rubber and filler particles, reduces the generation of hydrogen bonds, prevents the occurrence of continuous structural phenomenon, promotes the dispersion of the white carbon black in sizing materials, and obviously improves the mixing process and the storage stability;
(4) The presence of the vinyl active group in the BPDM prepared by the method ensures that after the BPDM flame retardant is blended with the silicone rubber, good interface binding force is generated between the BPDM flame retardant and the silicone rubber, and the BPDM flame retardant and the silicone rubber are tightly combined together. The good compatibility inevitably promotes the flame retardant to exhibit better dispersion in the silicone rubber, so that the flame retardant performance is improved, and meanwhile, the physical and mechanical properties such as tensile strength and the like are further improved;
(5) The synergistic flame-retardant system composed of the phosphorus and boron elements can obviously improve the flame-retardant efficiency of the synergistic flame-retardant system in the silicone rubber, and the lower additive amount of the flame retardant can ensure the stability of mechanical properties while the silicone rubber achieves ideal flame-retardant performance;
(6) The invention is accompanied by good flame retardant property and mechanical property, and the obtained flame retardant silicone rubber can be used for preparing cable accessory materials, such as high-pressure cold shrinkage type prefabricated parts.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The starting materials used in the examples below, unless otherwise specified, are all commercially available from conventional sources; the adopted technology adopts the conventional technology in the field unless specified otherwise; the operating temperatures employed, unless otherwise specified, were room temperature (20.+ -. 5 ℃ C.).
Example 1:
the flame-retardant silicone rubber material in the embodiment comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 40 parts of precipitated white carbon black, 15 parts of 3-hydroxyphenylboronic acid methyl iminodiacetate, 7.7 parts of bis (diethylamino) phosphoryl chloride, 2.3 parts of vinyl triacetoxy silane and two to five 5 parts of bis (diethylamino) phosphoryl chloride.
Wherein the number average molecular weight of the methyl vinyl silicone rubber is 56 ten thousand, the vinyl content is 0.25%, and the volatile component is less than or equal to 3.0%; the purity of the 3-hydroxyphenylborate methyl iminodiacetic acid ester is more than or equal to 96 percent, and the acidity coefficient is 3.7 to 4.1pKa; the purity of the bis (diethylamino) phosphoryl chloride is more than or equal to 95 percent, and the water content is less than or equal to 0.5 percent; the content of the effective substances of the vinyl triacetoxy silane is more than or equal to 95 percent;
the specific preparation method of the flame-retardant silicone rubber material comprises the following steps:
(1) Adding 3-hydroxyphenylboronic acid methyl iminodiacetic acid ester with a formula amount into a three-mouth bottle, dripping dimethylformamide into the three-mouth bottle, stirring and dissolving the three-mouth bottle, wherein the stirring and dissolving temperature is controlled at 30 ℃, and the stirring time is 18min.
(2) Gradually adding the corresponding bis (diethylamino) phosphoryl chloride, mixing at 50 ℃ for 6 hours, filtering the reaction product after the reaction, washing with distilled water, and drying in an oven at 105 ℃ for 2 hours.
(3) And (3) putting the reaction product into an F-type high-speed dispersing machine, adding the formula amount of vinyl triacetoxy silane, setting the stirring speed to be 1200r/min, and stirring for 12s to obtain the phosphorus-boron synergistic flame retardant BPDM.
(4) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 35 ℃, adjusting the mixing roller spacing to 4.0mm, and beginning plasticating;
(5) After plasticating is completed, adding the formula amount of white carbon black and BPDM into the silicone rubber for 5 times, wherein the adding interval time is 8min;
(6) Adding a double-penta vulcanizing agent into the rubber compound, adjusting the roll gap to 3mm, and carrying out mixing and sheet discharging in a triangle bag mode;
(7) And vulcanizing the rubber sheet obtained after the mixing is finished, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 12MPa, and the vulcanization time is 7min, so as to obtain the flame-retardant silicone rubber material.
Example 2:
the flame-retardant silicone rubber material in the embodiment comprises the following raw materials in parts by weight: 80 parts of methyl vinyl silicone rubber with the number average molecular weight of 52 ten thousand, 20 parts of methyl vinyl silicone rubber with the number average molecular weight of 63 ten thousand, 35 parts of fumed silica, 25.6 parts of 3-hydroxyphenylboric acid methyl iminodiacetate, 10.3 parts of bis (diethylamino) phosphoryl chloride, 4.1 parts of vinyl triacetoxy silane and 4.5 parts of bis (di-penta) phosphorus.
Wherein, the methyl vinyl silicone rubber with the number average molecular weight of 52 ten thousand has the vinyl content of 0.21 percent and the volatile component of less than or equal to 3.0 percent; methyl vinyl silicone rubber with the number average molecular weight of 63 ten thousand, the vinyl content of 0.28 percent and the volatile component of less than or equal to 3.0 percent; the purity of the 3-hydroxyphenylborate methyl iminodiacetic acid ester is more than or equal to 96 percent, and the acidity coefficient is 3.7 to 4.1pKa; the purity of the bis (diethylamino) phosphoryl chloride is more than or equal to 95 percent, and the water content is less than or equal to 0.5 percent; the content of the effective substances of the vinyl triacetoxy silane is more than or equal to 95 percent;
the specific preparation method of the flame-retardant silicone rubber material comprises the following steps:
(1) Adding 3-hydroxyphenylboronic acid methyl iminodiacetic acid ester with a formula amount into a three-mouth bottle, dripping dimethylformamide into the three-mouth bottle, stirring and dissolving the three-mouth bottle, wherein the stirring and dissolving temperature is controlled at 30 ℃, and the stirring time is 18min.
(2) Gradually adding the corresponding bis (diethylamino) phosphoryl chloride, mixing at 50 ℃ for 6 hours, filtering the reaction product after the reaction, washing with distilled water, and drying in an oven at 105 ℃ for 2 hours.
(3) And (3) putting the reaction product into an F-type high-speed dispersing machine, adding the formula amount of vinyl triacetoxy silane, setting the stirring speed to be 1200r/min, and stirring for 12s to obtain the phosphorus-boron synergistic flame retardant BPDM.
(4) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 35 ℃, adjusting the mixing roller spacing to 4.0mm, and beginning plasticating;
(5) After plasticating is completed, adding the white carbon black and the BPDM according to the formula amount into the silicon rubber for 5 times, wherein the adding interval time is 8min;
(6) Adding a double-penta vulcanizing agent into the rubber compound, adjusting the roll gap to 3mm, and carrying out mixing and sheet discharging in a triangle bag mode;
(7) And vulcanizing the rubber sheet obtained after the mixing is finished, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 12MPa, and the vulcanization time is 7min, so as to obtain the flame-retardant silicone rubber material.
Example 3:
the flame-retardant silicone rubber material in the embodiment comprises the following raw materials in parts by weight: 40 parts of methyl vinyl silicone rubber with the number average molecular weight of 52 ten thousand, 60 parts of methyl vinyl silicone rubber with the number average molecular weight of 63 ten thousand, 20 parts of precipitated white carbon black, 25 parts of gas-phase white carbon black, 23.4 parts of 3-hydroxyphenylboric acid methyl iminodiacetate, 7.8 parts of bis (diethylamino) phosphoryl chloride, 3.8 parts of vinyl triacetoxy silane and two to five 6 parts.
In the formula of the cable accessory material in the embodiment, the methyl vinyl silicone rubber with the number average molecular weight of 52 ten thousand has the vinyl content of 0.21 percent and the volatile component of less than or equal to 3.0 percent; methyl vinyl silicone rubber with the number average molecular weight of 63 ten thousand, the vinyl content of 0.28 percent and the volatile component of less than or equal to 3.0 percent; the purity of the 3-hydroxyphenylborate methyl iminodiacetic acid ester is more than or equal to 96 percent, and the acidity coefficient is 3.7 to 4.1pKa; the purity of the bis (diethylamino) phosphoryl chloride is more than or equal to 95 percent, and the water content is less than or equal to 0.5 percent; the content of the effective substances of the vinyl triacetoxy silane is more than or equal to 95 percent;
the specific preparation method of the flame-retardant silicone rubber material comprises the following steps:
(1) Adding 3-hydroxyphenylboronic acid methyl iminodiacetic acid ester with a formula amount into a three-mouth bottle, dripping dimethylformamide into the three-mouth bottle, stirring and dissolving the three-mouth bottle, wherein the stirring and dissolving temperature is controlled at 30 ℃, and the stirring time is 18min.
(2) Gradually adding the corresponding bis (diethylamino) phosphoryl chloride, mixing at 50 ℃ for 6 hours, filtering the reaction product after the reaction, washing with distilled water, and drying in an oven at 105 ℃ for 2 hours.
(3) And (3) putting the reaction product into an F-type high-speed dispersing machine, adding the formula amount of vinyl triacetoxy silane, setting the stirring speed to be 1200r/min, and stirring for 12s to obtain the phosphorus-boron synergistic flame retardant BPDM.
(4) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 35 ℃, adjusting the mixing roller spacing to 4.0mm, and beginning plasticating;
(5) After plasticating is completed, adding the white carbon black and the BPDM according to the formula amount into the silicon rubber for 5 times, wherein the adding interval time is 8min;
(6) Adding a double-penta vulcanizing agent into the rubber compound, adjusting the roll gap to 3mm, and carrying out mixing and sheet discharging in a triangle bag mode;
(7) And vulcanizing the rubber sheet obtained after the mixing is finished, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 12MPa, and the vulcanization time is 7min, so as to obtain the flame-retardant silicone rubber material.
Comparative example 1:
this comparative example differs from example 1 in that 3-hydroxyphenylboronic acid methyl iminodiacetate, bis (diethylamino) phosphoryl chloride and vinyltriacetoxy silane were omitted; the flame-retardant silicone rubber cable accessory material in the comparative example comprises the following manufacturing raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 40 parts of precipitated white carbon black and two to five 5 parts.
In the rubber material formula in the comparative example, the number average molecular weight of the methyl vinyl silicone rubber is 56 ten thousand, the vinyl content is 0.25%, and the volatile component is less than or equal to 3.0%;
the specific preparation method of the flame-retardant silicone rubber comprises the following steps:
(1) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 35 ℃, adjusting the mixing roller spacing to 4.0mm, and beginning plasticating;
(2) After plasticating is completed, adding the formula amount of white carbon black into the silicon rubber for 5 times, wherein the interval time is 8min;
(3) Adding a double-penta vulcanizing agent into the rubber compound, adjusting the roll gap to 3mm, and carrying out mixing and sheet discharging in a triangle bag mode;
(4) And vulcanizing the rubber sheet obtained after the mixing is finished, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 12MPa, and the vulcanization time is 7min, so that the flame-retardant silicone rubber material is obtained.
Comparative example 2:
the main difference between this comparative example and example 2 is that 10.3 parts of bis (diethylamino) phosphoryl chloride and 4.1 parts of vinyltriacetoxy silane are replaced by 3-hydroxyphenylboronic acid methyl iminodiacetate in equal amounts. The flame-retardant silicone rubber material in the comparative example comprises the following manufacturing raw materials in parts by weight: 80 parts of methyl vinyl silicone rubber with the number average molecular weight of 52 ten thousand, 20 parts of methyl vinyl silicone rubber with the number average molecular weight of 63 ten thousand, 35 parts of fumed silica, 40 parts of 3-hydroxyphenylboric acid methyl iminodiacetate and twenty-five 4.5 parts.
In the cable accessory material formula in the comparative example, the methyl vinyl silicone rubber with the number average molecular weight of 52 ten thousand has the vinyl content of 0.21 percent and the volatile component of less than or equal to 3.0 percent; methyl vinyl silicone rubber with the number average molecular weight of 63 ten thousand, the vinyl content of 0.28 percent and the volatile component of less than or equal to 3.0 percent; the purity of the 3-hydroxyphenylborate methyl iminodiacetic acid ester is more than or equal to 96 percent, and the acidity coefficient is 3.7 to 4.1pKa;
the specific preparation method of the flame-retardant silicone rubber comprises the following steps:
(1) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 35 ℃, adjusting the mixing roller spacing to 4.0mm, and beginning plasticating;
(2) After plasticating is completed, adding the formula amount of white carbon black and 3-hydroxyphenylborate methyl iminodiacetic acid ester into the silicon rubber for 5 times, wherein the interval time is 8min;
(6) Adding a double-penta vulcanizing agent into the rubber compound, adjusting the roll gap to 3mm, and carrying out mixing and sheet discharging in a triangle bag mode;
(7) And vulcanizing the rubber sheet obtained after the mixing is finished, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 12MPa, and the vulcanization time is 7min, so as to obtain the flame-retardant silicone rubber material.
Comparative example 3:
the main difference between this comparative example and example 2 is that 25.6 parts of 3-hydroxyphenylboronic acid methyliminodiacetate and 4.1 parts of vinyltriacetoxysilane are replaced by equivalent amounts of bis (diethylamino) phosphoryl chloride. The flame-retardant silicone rubber cable accessory material in the comparative example comprises the following manufacturing raw materials in parts by weight: 80 parts of methyl vinyl silicone rubber with the number average molecular weight of 52 ten thousand, 20 parts of methyl vinyl silicone rubber with the number average molecular weight of 63 ten thousand, 35 parts of fumed silica, 40 parts of bis (diethylamino) phosphoryl chloride and twenty-five 4.5 parts of bis (diethylamino) phosphoryl chloride.
In the cable accessory material formula in the comparative example, the methyl vinyl silicone rubber with the number average molecular weight of 52 ten thousand has the vinyl content of 0.21 percent and the volatile component of less than or equal to 3.0 percent; methyl vinyl silicone rubber with the number average molecular weight of 63 ten thousand, the vinyl content of 0.28 percent and the volatile component of less than or equal to 3.0 percent; the purity of the bis (diethylamino) phosphoryl chloride is more than or equal to 95 percent, and the water content is less than or equal to 0.5 percent;
the specific preparation method of the flame-retardant silicone rubber material comprises the following steps:
(1) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 35 ℃, adjusting the mixing roller spacing to 4.0mm, and beginning plasticating;
(2) After plasticating is completed, adding the formula amount of white carbon black and bis (diethylamino) phosphoryl chloride into the silicon rubber for 5 times, wherein the interval time is 8min;
(6) Adding a double-penta vulcanizing agent into the rubber compound, adjusting the roll gap to 3mm, and carrying out mixing and sheet discharging in a triangle bag mode;
(7) And vulcanizing the rubber sheet obtained after the mixing is finished, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 12MPa, and the vulcanization time is 7min, so as to obtain the flame-retardant silicone rubber material.
Comparative example 4:
the main difference between this comparative example and example 3 is that 3.8 parts of vinyltriacetoxysilane are reacted with 3-hydroxyphenylboronic acid methyliminodiacetate and bis (diethylamino) phosphoryl chloride in a ratio of 3:1 are replaced in equal amounts. The flame-retardant silicone rubber cable accessory material in the comparative example comprises the following manufacturing raw materials in parts by weight: 40 parts of methyl vinyl silicone rubber with the number average molecular weight of 52 ten thousand, 60 parts of methyl vinyl silicone rubber with the number average molecular weight of 63 ten thousand, 20 parts of precipitated white carbon black, 25 parts of gas-phase white carbon black, 26.3 parts of 3-hydroxyphenylboric acid methyl iminodiacetate, 8.7 parts of bis (diethylamino) phosphoryl chloride and twenty-five 6 parts.
In the cable accessory material formula in the comparative example, the methyl vinyl silicone rubber with the number average molecular weight of 52 ten thousand has the vinyl content of 0.21 percent and the volatile component of less than or equal to 3.0 percent; methyl vinyl silicone rubber with the number average molecular weight of 63 ten thousand, the vinyl content of 0.28 percent and the volatile component of less than or equal to 3.0 percent; the purity of the 3-hydroxyphenylborate methyl iminodiacetic acid ester is more than or equal to 96 percent, and the acidity coefficient is 3.7 to 4.1pKa; the purity of the bis (diethylamino) phosphoryl chloride is more than or equal to 95 percent, and the water content is less than or equal to 0.5 percent;
the specific preparation method of the flame-retardant silicone rubber material comprises the following steps:
(1) Adding 3-hydroxyphenylboronic acid methyl iminodiacetic acid ester with a formula amount into a three-mouth bottle, dripping dimethylformamide into the three-mouth bottle, stirring and dissolving the three-mouth bottle, wherein the stirring and dissolving temperature is controlled at 30 ℃, and the stirring time is 18min.
(2) Gradually adding corresponding bis (diethylamino) phosphoryl chloride, mixing at 50 ℃ for 6 hours, filtering the reaction product after the reaction is finished, washing with distilled water, and drying in an oven at 105 ℃ for 2 hours to obtain the phosphorus-boron flame retardant.
(4) The methyl vinyl silicone rubber with the formula amount is placed on an open mill with the roller temperature of 35 ℃, the mixing roller spacing is adjusted to 4.0mm, and plasticating is started.
(5) After plasticating, adding the white carbon black and the phosphorus-boron flame retardant into the silicon rubber for 5 times at intervals of 8 minutes.
(6) And adding a double-di-penta vulcanizing agent into the rubber compound, adjusting the roll gap to 3mm, and carrying out mixing and sheet discharging in a triangle bag mode.
(7) And vulcanizing the rubber sheet obtained after the mixing is finished, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 12MPa, and the vulcanization time is 7min, so as to obtain the flame-retardant silicone rubber material.
Comparative example 5:
the main difference between this comparative example and example 3 is that the formulation amounts of 3-hydroxyphenylboronic acid methyl iminodiacetate, bis (diethylamino) phosphoryl chloride and vinyltriacetoxy silane were directly added to the mill for blending with the silicone rubber. The flame-retardant silicone rubber cable accessory material in the comparative example comprises the following manufacturing raw materials in parts by weight: 40 parts of methyl vinyl silicone rubber with the number average molecular weight of 52 ten thousand, 60 parts of methyl vinyl silicone rubber with the number average molecular weight of 63 ten thousand, 20 parts of precipitated white carbon black, 25 parts of gas-phase white carbon black, 23.4 parts of 3-hydroxyphenylboric acid methyl iminodiacetate, 7.8 parts of bis (diethylamino) phosphoryl chloride, 3.8 parts of vinyl triacetoxy silane and two to five 6 parts.
In the cable accessory material formula in the comparative example, the methyl vinyl silicone rubber with the number average molecular weight of 52 ten thousand has the vinyl content of 0.21 percent and the volatile component of less than or equal to 3.0 percent; methyl vinyl silicone rubber with the number average molecular weight of 63 ten thousand, the vinyl content of 0.28 percent and the volatile component of less than or equal to 3.0 percent; the purity of the 3-hydroxyphenylborate methyl iminodiacetic acid ester is more than or equal to 96 percent, and the acidity coefficient is 3.7 to 4.1pKa; the purity of the bis (diethylamino) phosphoryl chloride is more than or equal to 95 percent, and the water content is less than or equal to 0.5 percent; the content of the effective substances of the vinyl triacetoxy silane is more than or equal to 95 percent;
the specific preparation method of the flame-retardant silicone rubber material comprises the following steps:
(1) The methyl vinyl silicone rubber with the formula amount is placed on an open mill with the roller temperature of 35 ℃, the mixing roller spacing is adjusted to 4.0mm, and plasticating is started.
(5) After plastication is completed, the formula amounts of white carbon black, 3-hydroxyphenylboronic acid methyl iminodiacetate, bis (diethylamino) phosphoryl chloride and vinyltriacetoxy silane are added into the silicone rubber 5 times at intervals of 8 minutes.
(6) And adding a double-di-penta vulcanizing agent into the rubber compound, adjusting the roll gap to 3mm, and carrying out mixing and sheet discharging in a triangle bag mode.
(7) Vulcanizing the rubber sheet obtained after mixing, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 12MPa, and the vulcanization time is 7min, so that the flame-retardant silicone rubber cable accessory material is obtained.
And (3) detection:
(1) Physical and mechanical property test
The flame retardant silicone rubber materials prepared in examples 1 to 3 and comparative examples 1 to 5 were respectively tested for physical and mechanical properties according to the test methods described in the standards in table 1, and the test results are recorded in table 1 below.
Table 1 results of physical mechanical property test of flame retardant silicone rubber cable accessory materials in examples 1 to 3 and comparative examples 1 to 5
As can be seen from the test results in Table 1, the overall physical and mechanical properties of the flame retardant silicone rubber cable accessory materials in examples 1 to 3 of the present invention are better than those of the flame retardant silicone rubber materials in comparative examples 1 to 5. Due to the existence of vinyl active groups, after the BPDM phosphorus boron synergistic flame retardant generated by the reaction of the 3-hydroxyphenylboric acid methyl iminodiacetic acid ester, the bis (diethylamino) phosphoryl chloride and the vinyl triacetoxy silane under certain conditions is blended with the silicone rubber, good interface binding force is generated between the two agents, the two agents are tightly combined together due to good compatibility, and the stability of physical and mechanical properties such as tensile strength and the like is realized while the flame retardant requirement of cable accessory materials is met with less addition. In addition, BPDM is used as a low molecular organic compound containing boron, phosphorus and silicon, can act with Si-OH groups on the surface of white carbon black, improves the affinity between silicon rubber and filler particles, reduces the generation of hydrogen bonds, prevents the occurrence of continuous structural phenomenon, promotes the dispersion of the white carbon black in sizing material, prevents the sizing material from hardening, and obviously improves the mixing process and the storage stability.
(2) Flame retardant Performance test
The flame retardant properties of the flame retardant silicone rubber cable accessory materials prepared in examples 1 to 3 and comparative examples 1 to 5 were respectively tested according to the test methods described in the standards in table 2, and the test results are recorded in tables 2, 3 and 4, respectively. Tables 2 and 3 respectively test oxygen index, smoke density and UL94 self-extinguishing property of the flame retardant silicone rubber cable accessory material after vulcanization, and table 4 test flame retardant self-extinguishing property of the vulcanized spline after water bath treatment under the following water bath treatment conditions: placing the sample strip into a water bath with the constant temperature of 70 ℃ for 120 hours, then wiping the sample strip, drying the sample strip for 30 minutes at the temperature of 110 ℃, cooling the sample strip to the room temperature, performing a vertical burning test on the sample strip, and judging the flame retardant level of the sample strip after the sample strip is boiled in water.
Table 2 flame retardant property test results of flame retardant silicone rubber cable accessory materials in examples 1 to 3 and comparative examples 1 to 5
Table 3 results of self-extinguishing test of flame retardant silicone rubber cable accessory materials in examples 1 to 3 and comparative examples 1 to 5
Table 4 results of self-extinguishing test of the flame retardant silicone rubber cable accessory materials of examples 1 to 3 and comparative examples 1 to 5 after passing through 70 c x 120h water bath
As can be seen from Table 2, the flame retardant silicone rubber cable accessory materials obtained in examples 1 to 3 of the present invention have a higher oxygen index and a lower smoke density. As shown by the test results of various flame retardant properties in tables 3 and 4, in the two states of no water bath treatment and 70 ℃ multiplied by 120h water bath treatment, samples are not burnt out in the two flame-retarding processes, the dropping phenomenon is avoided, meanwhile, the cotton at the bottom can not be ignited, the two-time combustion can reach the state of being out of fire, the phenomenon can fully indicate that BPDM flame retardant can be dehydrated into a ring after being heated, a boron-oxygen six-membered ring network structure is formed, more carbon layers containing B-O-C bonds can be formed after the structure is further combusted, the formation of the carbide can block heat transfer, and the silicon rubber is prevented from being further oxidized.
The BPDM flame retardant containing phosphorus atoms can generate phosphoric acid in the heating process, and the phosphoric acid can be condensed with a C-O bond to form polyphosphoric acid crosslinking, and can also form stable BPO with boron element at high temperature 4 Both are catalyzed together to formThe compact protective carbon layer of the catalyst can minimize the generation of gas phase products and carbonyl compounds.
Compared with three single-class organic compounds of directly adding 3-hydroxyphenylboronic acid methyl iminodiacetate, bis (diethylamino) phosphoryl chloride and vinyl triacetoxy silane, three elements of phosphorus, boron and silicon are constructed together under certain conditions, and the formed BPDM phosphorus-boron synergistic flame retardant can necessarily realize higher flame retardant efficiency with lower addition amount. The good compatibility and dispersion of BPDM creates more possibilities for dual promotion of flame retardant and physical mechanical properties of silicone rubber cable accessory materials.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The flame-retardant silicone rubber material is characterized by being prepared from the following raw materials in parts by weight: 100-110 parts of silicon rubber, 20-40 parts of filler, 10-45 parts of phosphorus-boron synergistic flame retardant and 2-7 parts of vulcanizing agent;
wherein the phosphorus-boron synergistic flame retardant is prepared from 3-hydroxyphenylborate methyl iminodiacetate, bis (diethylamino) phosphoryl chloride and vinyl triacetoxy silane according to the mass ratio of 1.1-3.5: 1: and (3) carrying out a compounding reaction at 0.2-0.6.
2. A flame retardant silicone rubber material according to claim 1, characterized in that: the silicone rubber is methyl vinyl silicone rubber; the filler is white carbon black; the vulcanizing agent is two to five.
3. A method for preparing the flame retardant silicone rubber material according to any one of claims 1 to 2, comprising the steps of:
(1) Dropwise adding dimethyl formamide into 3-hydroxyphenylboronic acid methyl iminodiacetic acid ester to stir and dissolve, so as to obtain a dissolving solution for standby;
(2) Adding bis (diethylamino) phosphoryl chloride into the solution, carrying out suction filtration after mixing reaction, washing, and drying to obtain a dried product for later use;
(3) Adding the dried product into vinyl triacetoxy silane, and stirring and dispersing to obtain a phosphorus-boron synergistic flame retardant;
(4) Placing the silicon rubber on an open mill, starting plasticating, adding a filler and a phosphorus-boron synergistic flame retardant for mixing after plasticating is finished, and obtaining a mixed rubber;
(5) And adding a vulcanizing agent into the rubber compound, mixing, blanking, and vulcanizing the rubber sheet to obtain the flame-retardant silicone rubber material.
4. A method for preparing a flame retardant silicone rubber material according to claim 3, characterized in that: the temperature of stirring and dissolving in the step (1) is 30 ℃, and the stirring time is 15-20min.
5. A method for preparing a flame retardant silicone rubber material according to claim 3, characterized in that: the temperature of the mixing reaction in the step (2) is 40-55 ℃, the reaction time is 4-7h, and the drying mode is drying in an oven at 105 ℃ for 2h.
6. A method for preparing a flame retardant silicone rubber material according to claim 3, characterized in that: the stirring and dispersing rotational speed in the step (3) is 1000-1500 r/min, and the stirring time is 10-15s.
7. A method for preparing a flame retardant silicone rubber material according to claim 3, characterized in that: and (3) setting the mixing temperature of the open mill in the step (4) to be 30-40 ℃, and adjusting the mixing roll gap to be 4-5 mm.
8. A method for preparing a flame retardant silicone rubber material according to claim 3, characterized in that: the filler and the phosphorus-boron synergistic flame retardant in the step (4) are added for 3-6 times, and the interval between each addition is 2-8 min.
9. A method for preparing a flame retardant silicone rubber material according to claim 3, characterized in that: the mode of mixing and discharging sheets in the step (5) is to adjust the roll spacing to 2-3 mm, mixing and discharging sheets are carried out in a triangle bag mode, the vulcanization temperature is 170-180 ℃, the vulcanization pressure is 10-15MPa, and the vulcanization time is 3-10min.
10. Use of a flame retardant silicone rubber material according to any one of claims 1-2 for the preparation of a high voltage cable accessory material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311849497.XA CN117866443A (en) | 2023-12-29 | 2023-12-29 | Flame-retardant silicone rubber material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311849497.XA CN117866443A (en) | 2023-12-29 | 2023-12-29 | Flame-retardant silicone rubber material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117866443A true CN117866443A (en) | 2024-04-12 |
Family
ID=90596284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311849497.XA Pending CN117866443A (en) | 2023-12-29 | 2023-12-29 | Flame-retardant silicone rubber material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117866443A (en) |
-
2023
- 2023-12-29 CN CN202311849497.XA patent/CN117866443A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111057367B (en) | High-lasting flame-retardant nylon 6 and preparation method thereof | |
| CN110467779A (en) | A kind of harsh cable high-performance synthetic rubber of three generations's nuclear power station and preparation method thereof | |
| CN114702749A (en) | Flame-retardant polyolefin and preparation method thereof | |
| CN112812571A (en) | Fireproof and arc-resistant silicon rubber, preparation method thereof and fireproof and arc-resistant adhesive tape | |
| CN114656702B (en) | Flame-retardant rubber for building safety net and preparation method thereof | |
| CN109054395B (en) | High-temperature-resistant halogen-free flame-retardant silicone rubber and preparation method thereof | |
| CN115011078A (en) | Flame-retardant environment-friendly PET plastic and preparation method thereof | |
| CN114181536A (en) | Flame-retardant silicone rubber material and preparation method and application thereof | |
| CN117264316B (en) | Antistatic polyolefin composition and preparation method thereof | |
| CN113929992A (en) | Halogen-free flame-retardant CR foam and preparation method thereof | |
| CN113234315A (en) | Flame-retardant yellowing-resistant TPU cable material and preparation method and application thereof | |
| CN113429770A (en) | Preparation method of efficient flame-retardant modified unsaturated polyester resin | |
| CN117866443A (en) | Flame-retardant silicone rubber material and preparation method and application thereof | |
| CN117004127A (en) | Chitosan-based high-flame-retardance MPP pipe and preparation method thereof | |
| CN116874878A (en) | Flame retardant for ethylene propylene diene monomer and preparation method thereof | |
| CN110591213A (en) | Low-smoke-density high-flame-retardant halogen-free cable material and preparation method thereof | |
| CN114507380B (en) | MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant and preparation method and application thereof | |
| CN115716985A (en) | Halogen-free flame-retardant polyurethane elastomer and preparation method thereof | |
| CN115246927B (en) | Graphene oxide-based phosphorus-nitrogen-silicon composite flame-retardant copolyester and preparation method thereof | |
| CN115746446A (en) | CPR-grade silane crosslinking flame-retardant polyolefin cable material for photovoltaic cable and preparation method thereof | |
| CN114891293A (en) | Halogen-free low-smoke flame-retardant cable material and preparation method thereof | |
| CN109535638B (en) | Flame-retardant smoke-suppression ABS for electronic equipment shell and preparation method thereof | |
| CN113736127A (en) | Flame-retardant EVA shoe material for casual shoes and preparation method thereof | |
| CN111073298A (en) | Flame-retardant plugging agent for substation and preparation method and use method thereof | |
| CN115785676B (en) | Flame-retardant silicone rubber material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |