CN114656700A - Flame-retardant chloroprene rubber and preparation method thereof - Google Patents
Flame-retardant chloroprene rubber and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of rubber materials, and particularly discloses flame-retardant chloroprene rubber and a preparation method thereof. The flame-retardant chloroprene rubber disclosed by the invention comprises the following raw materials: chloroprene rubber, trans-1, 4-butadiene-isoprene copolymer rubber, an accelerator, an anti-aging agent, stearic acid, white carbon black, zinc oxide and a flame retardant. The flame retardant, namely the functionalized magnesium hydroxide, prepared by the invention contains various flame retardant elements such as magnesium, phosphorus, nitrogen and the like, and is used as the flame retardant in the chloroprene rubber, so that the compatibility problem of the traditional flame retardant in the chloroprene rubber is solved, the processability and mechanical properties of the traditional chloroprene rubber material are improved, and the using amount of the flame retardant is greatly reduced.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to flame-retardant chloroprene rubber and a preparation method thereof.
Background
Chloroprene rubber is a homopolymerized elastomer prepared by free radical polymerization of 2-chloro-1, 3-butadiene as a monomer, and is classified into a sulfur regulation type, a non-sulfur regulation type and a mixed regulation type according to the regulation mode of molecular weight during polymerization. Neoprene is a multifunctional elastomer with many properties, such as moderate oil and weather resistance (uv, ozone), chemical corrosion resistance, abrasion resistance, good flex crack resistance, low compression set, and good resilience after compression. Neoprene can be divided into five categories according to the application, which are respectively: general purpose chloroprene rubber of G type, general purpose chloroprene rubber of W type, chloroprene rubber for adhesion, polychloroprene latex, special purpose chloroprene rubber, are widely used in the fields such as conveyer belt, adhesive, wire and cable covering, rubber tube adhesive tape, gasket, etc.
The chloroprene rubber material is generally in a sheet shape or a block shape, and the color is milk white, beige and light brown. Because of easy crystallization, easy oriented crystallization during the process of drawing the material has good self-reinforcement. The molecular chain contains polar groups, the intermolecular interaction force is large, the tensile strength is high, but the tear strength is slightly poor. The weather resistance and the aging resistance are good, and the long-term use wear resistance is higher than that of natural rubber.
The electronic effect and volume effect of chlorine atoms in the chloroprene rubber can passivate carbon-carbon double bonds, a sulfur-accelerator system cannot be used for vulcanization, and only 1.5 percent of allyl groups with 1, 2-structures can be crosslinked under an alkali metal oxide (zinc oxide/magnesium oxide) system to generate C-O-C ether bonds. The chloroprene rubber has the problems of easy scorching, poor processability, poor fatigue resistance and other unbalanced comprehensive properties. In order to improve the processability, flame retardancy and fatigue resistance of chloroprene rubber, chloroprene rubber is usually chemically modified or blended with natural rubber, butadiene rubber and the like.
The invention patent of application number 201510219612.4 discloses a flame-retardant chloroprene material and a preparation method thereof, belonging to the technical field of rubber materials and preparation methods thereof. The invention comprises the following components in percentage by weight: 37-42% of chloroprene rubber, 12-16% of semi-reinforcing carbon black, 3.0-5.0% of zinc oxide, 2.6-4.6% of light magnesium oxide, 0.3-0.8% of stearic acid, 0.8-1.3% of 4,4' -bis (phenylisopropyl) diphenylamine, 0.1-0.3% of an accelerator Na-22, 0.3-0.7% of an accelerator DM, 8.0-12% of a flame retardant Chemimix FR-4, 3.0-6.0% of diantimony trioxide, 15-20% of aluminum hydroxide and 10-15% of a plasticizer D-810. The invention takes Chemimix FR-4 flame retardant as a main body, and simultaneously adds aluminum hydroxide and antimony trioxide to form a composite flame retardant, and the three are added into the chloroprene rubber material as a whole to achieve the flame retardant effect, but the flame retardant belongs to inorganic materials and has poor compatibility with organic materials of a matrix, so that the flame retardant property of the chloroprene rubber can not be fully exerted, and the problem of mechanical property reduction can be caused.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides flame-retardant chloroprene rubber and a preparation method thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
the flame-retardant chloroprene rubber is prepared from the following raw materials: chloroprene rubber, trans-1, 4-butadiene-isoprene copolymer rubber, an accelerator, an anti-aging agent, stearic acid, white carbon black, zinc oxide and a flame retardant.
The flame-retardant chloroprene rubber is prepared from the following raw materials: 70-85 parts of chloroprene rubber, 15-30 parts of trans-1, 4-butadiene-isoprene copolymer rubber, 1-3 parts of accelerator, 1-2 parts of anti-aging agent, 1-2 parts of stearic acid, 20-30 parts of white carbon black, 5-10 parts of zinc oxide and 8-15 parts of flame retardant.
The accelerator is any one of accelerator NA-22, accelerator MTT-80 and accelerator TMTD.
The anti-aging agent is any one of anti-aging agent 4020, anti-aging agent RD and anti-aging agent ODA.
The flame retardant is any one of magnesium hydroxide, modified magnesium hydroxide and functionalized magnesium hydroxide.
Magnesium hydroxide is widely used as an environment-friendly halogen-free flame retardant due to its high decomposition temperature, and its performance is mainly due to the following two factors: firstly, the magnesium hydroxide is decomposed at the temperature of more than 300 ℃ to generate combustible gas in a water vapor dilution gas phase, and secondly, a physical barrier consisting of a magnesium oxide layer can be formed in a condensed phase in the magnesium hydroxide decomposition process. However, when magnesium hydroxide is used as a one-component flame retardant, the flame retardant has problems of low flame retardant efficiency, poor dispersibility in a polymer matrix material, and the like.
Further, the flame retardant is modified magnesium hydroxide.
The preparation method of the modified magnesium hydroxide comprises the following steps:
s1, dispersing 25-40 parts by weight of magnesium hydroxide in 90-110 parts by weight of absolute ethyl alcohol to obtain a dispersion liquid a; adding 0.5-2 parts by weight of silane coupling agent into a mixed solution consisting of 10-20 parts by weight of water and 90-110 parts by weight of absolute ethyl alcohol, adjusting the pH to 2.5-4, and stirring at room temperature for 20-40min to obtain a solution b; dissolving 15-30 parts by weight of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in 30-40 parts by weight of absolute ethyl alcohol to obtain a solution c;
s2, adding the solution b into the dispersion liquid a under the nitrogen condition, continuously stirring at the rotation speed of 400rpm of 300-.
9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is used as a halogen-free phosphate flame retardant and has excellent gas-phase efficient flame retardance. DOPO has higher thermal stability, chemical stability, excellent flame retardancy and low toxicity due to the presence of a cyclic diphenyl phosphate group in its molecular structure, compared to other linear low molecular weight aliphatic phosphate esters and phosphorus compounds. In addition, because the DOPO molecules contain active P-H bonds, the DOPO molecules can better perform addition reaction with unsaturated groups, such as epoxy groups, Schiff bases, carbon-nitrogen double bonds and triple bonds, carbon-carbon double bonds and the like, so that the DOPO molecules can be used for synthesizing various types of DOPO-based synergistic flame retardants and smoke suppressants.
Still further, the flame retardant is functionalized magnesium hydroxide.
The preparation method of the functionalized magnesium hydroxide comprises the following steps:
s1, dispersing 25-40 parts by weight of magnesium hydroxide in 90-110 parts by weight of absolute ethyl alcohol to obtain a dispersion liquid a; adding 0.5-2 parts by weight of silane coupling agent into a mixed solution consisting of 10-20 parts by weight of water and 90-110 parts by weight of absolute ethyl alcohol, adjusting the pH to 2.5-4, and stirring at room temperature for 20-40min to obtain a solution b; dissolving 15-30 parts by weight of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in 30-40 parts by weight of absolute ethyl alcohol to obtain a solution c;
s2, adding the solution b into the dispersion liquid a under the condition of nitrogen, continuously stirring at the rotation speed of 400rpm of 300-;
s3, uniformly mixing 10-15 parts by weight of melamine, 15-25 parts by weight of formaldehyde, 15-25 parts by weight of n-butanol and 15-25 parts by weight of water, adjusting the pH to 8-9, and stirring at the temperature of 65-80 ℃ and the rotating speed of 700-1000rpm for 20-40min to obtain a melamine formaldehyde resin prepolymer solution;
s4, adding the whole melamine formaldehyde resin prepolymer solution obtained in the step S3, 0.5-2 parts by weight of dispersant and 30-45 parts by weight of modified magnesium hydroxide obtained in the step S2 into 80-120 parts by weight of water, stirring at the rotation speed of 400-65 rpm for 50-80min at the temperature of 55-65 ℃, cooling to room temperature, adjusting the pH value to 8-10, continuing to stir for 20-40min, filtering, washing and drying to obtain the functionalized magnesium hydroxide.
The silane coupling agent is any one of vinyl triethoxysilane and gamma- (2, 3-epoxypropane) propyl trimethoxysilane-diethylenetriaminopropyl trimethoxysilane.
The dispersing agent is sodium dodecyl sulfate and/or polyoxyethylene octyl phenol ether.
The dispersing agent is a mixture of sodium dodecyl sulfate and polyoxyethylene octyl phenol ether, wherein the mass ratio of the sodium dodecyl sulfate to the polyoxyethylene octyl phenol ether is (2-5): 1.
The invention adopts the sodium dodecyl sulfate and the polyoxyethylene octyl phenol ether as the dispersing agent together, and the sodium dodecyl sulfate and the polyoxyethylene octyl phenol ether are both surfactants, so that the interfacial tension can be effectively reduced; meanwhile, the lauryl sodium sulfate can be adsorbed on the surface of the modified magnesium hydroxide solid, so that the wettability of the modified magnesium hydroxide solid is improved, the dispersion condition of the modified magnesium hydroxide solid is improved, the particle size of the microsphere is reduced, and the particle size distribution is more uniform; and the polyoxyethylene octyl phenol ether has a charge effect which can keep and control fine resin particles precipitated from a continuous phase to be uniformly precipitated on the surface of the modified magnesium hydroxide to form a capsule wall, and regulate and control the polymerization reaction of the melamine formaldehyde resin. The two components act together to promote the prepared functionalized magnesium hydroxide microcapsule to have no adhesion phenomenon, good compactness and complete sphere.
The melamine formaldehyde resin is also an environment-friendly nitrogen-based flame retardant and has excellent thermal stability. Although the melamine formaldehyde resin cannot directly react with magnesium hydroxide and/or 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a prepolymer thereof may be adsorbed on the surface of magnesium hydroxide and/or 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide by a sol-gel method to form a shell on the surface of magnesium hydroxide and/or 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. The melamine formaldehyde resin of the invention forms a magnesium-phosphorus-nitrogen (Mg-P-N) synergistic system with magnesium hydroxide and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and shows better flame retardant performance than a single-core shell encapsulated flame retardant.
The method comprises the steps of firstly carrying out hydrolysis reaction on silane coupling agent and magnesium hydroxide under an acidic condition to obtain vinyl magnesium hydroxide, then carrying out nucleophilic addition reaction on the vinyl magnesium hydroxide and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to obtain modified magnesium hydroxide, carrying out nucleophilic addition reaction on melamine and formaldehyde under a heating alkaline condition to generate water-soluble melamine formaldehyde resin prepolymer, and adsorbing the water-soluble melamine formaldehyde resin prepolymer on the surface of the modified magnesium hydroxide by a sol-gel method, so that a shell is formed on the surface of the modified magnesium hydroxide, and obtaining the functionalized magnesium hydroxide with a core-double-shell structure.
The flame retardant mechanism of the present invention may be attributed to the following three points: 1) the P-C bond in the functionalized magnesium hydroxide is broken to generate an acidic substance, and particularly at high temperature, such as phosphoric acid and polyphosphoric acid, vermicular carbon can be combined together, so that the gaps among carbon layers are reduced, and a compact, continuous and expanded carbon layer is formed; 2) the endothermic decomposition of magnesium hydroxide in the functionalized magnesium hydroxide releases high-temperature water vapor, can dilute hot air and cool the surface of a pyrolysis area, and generates a magnesium oxide carbon residue layer with a physical protection function; 3) the decomposition of melamine formaldehyde resin in the functionalized magnesium hydroxide will release non-combustible gases (such as NO) during combustionx) Thereby diluting the combustible gas and oxygen concentration surrounding the material. Therefore, the functional magnesium hydroxide prepared by the invention shows better synergistic flame retardant effect when being blended into chloroprene rubber.
A preparation method of flame-retardant chloroprene rubber comprises the following steps:
(1) the chloroprene rubber and the trans-1, 4-butadiene-isoprene copolymer rubber are put into an internal mixer, roll-coating plastication is carried out for 10-20min, then the anti-aging agent, the stearic acid, the white carbon black, the flame retardant, the accelerator and the zinc oxide are sequentially added, and rubber is discharged after mixing for 15-45min, so as to obtain rubber compound;
(2) and (2) vulcanizing the rubber compound obtained in the step (1) on a flat vulcanizing machine to obtain the flame-retardant chloroprene rubber.
The vulcanization conditions are as follows: the temperature is 160-175 ℃, the pressure is 10-20MPa, and the time is 10-30 min.
The invention has the beneficial effects that:
1. the functional magnesium hydroxide prepared by the invention is a core-double shell structure microcapsule, contains multiple flame retardant elements such as magnesium, phosphorus, nitrogen and the like, is used as a flame retardant for chloroprene rubber, not only reduces the dosage and cost of the flame retardant, but also can form a compact protective layer through the decomposition of a magnesium-phosphorus-nitrogen system through a heat absorption process so as to inhibit oxygen (O)2) And heat enters the material body, so that the excellent synergistic flame retardant property is obtained.
2. The flame retardant prepared by the invention improves the compatibility problem of the traditional flame retardant in chloroprene rubber, improves the processing performance and mechanical performance of the traditional flame-retardant chloroprene rubber material, greatly reduces the using amount of the flame retardant, has excellent flame retardant performance, can adapt to specific use places, and has good market prospect.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
neoprene, grade: S40V, product of Nippon Denshoku industries Co., Ltd.
Trans-1, 4-butadiene-isoprene copolymer rubber, trans-1, 4-structure>92% (mol), butadiene unit content 17.3% (mol), molecular weight MW=77 ten thousand, supplied by Shandong Hua Polymer materials Co. Trans-1, 4-butadiene-isoprene copolymer rubber (TBIR) is a novel synthetic rubber material, and has high green strength and excellent fatigue resistance.
9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, CAS No.: 35948-25-5.
Accelerator MTT-80, the main components are: 3-methyl-2-thiazolethione, effective content: 80% by Attman New Material science and technology, Inc.
The anti-aging agent 4020 is provided by Shijiazhuang Zhongde chemical science and technology Co.
White carbon black, mesh number: 100 meshes, provided by Daokang mineral products Limited, Hebei province.
Magnesium hydroxide, density: 2.36g/cm3Supplied by Shanghai Kenren chemical Co., Ltd.
Gamma- (2, 3-epoxypropane) propyltrimethoxysilane, CAS no: 2530-83-8.
Polyoxyethylene octyl phenol ether, HLB value: 14.5, provided by Hubei Boshi chemical Co., Ltd.
Example 1
The flame-retardant chloroprene rubber consists of the following raw materials: 80 parts of chloroprene rubber, 20 parts of trans-1, 4-butadiene-isoprene copolymer rubber, 2 parts of accelerator, 1.5 parts of anti-aging agent, 1.5 parts of stearic acid, 25 parts of white carbon black, 8 parts of zinc oxide and 10 parts of flame retardant.
The accelerator is an accelerator MTT-80.
The anti-aging agent is an anti-aging agent 4020.
The flame retardant is magnesium hydroxide.
A preparation method of flame-retardant chloroprene rubber comprises the following steps:
(1) the chloroprene rubber and the trans-1, 4-butadiene-isoprene copolymer rubber are put into an internal mixer, roll-coating plastication is carried out for 15min, then the anti-aging agent, the stearic acid, the white carbon black, the flame retardant, the accelerator and the zinc oxide are sequentially added, and rubber tapping is carried out after mixing for 30min, so as to obtain rubber compound;
(2) and (3) vulcanizing the rubber compound obtained in the step (1) on a flat vulcanizing machine to obtain the flame-retardant chloroprene rubber.
The vulcanization conditions are as follows: the temperature is 165 ℃, the pressure is 15MPa, and the time is 15 min.
Example 2
The flame-retardant chloroprene rubber is prepared from the following raw materials: 80 parts of chloroprene rubber, 20 parts of trans-1, 4-butadiene-isoprene copolymer rubber, 2 parts of accelerator, 1.5 parts of anti-aging agent, 1.5 parts of stearic acid, 25 parts of white carbon black, 8 parts of zinc oxide and 10 parts of flame retardant.
The accelerator is an accelerator MTT-80.
The anti-aging agent is an anti-aging agent 4020.
The flame retardant is modified magnesium hydroxide.
The preparation method of the modified magnesium hydroxide comprises the following steps:
s1, dispersing 30 parts by weight of magnesium hydroxide in 100 parts by weight of absolute ethyl alcohol to obtain a dispersion liquid a; adding 1 part by weight of gamma- (2, 3-epoxypropane) propyl trimethoxy silane into a mixed solution consisting of 15 parts by weight of water and 100 parts by weight of absolute ethyl alcohol, adjusting the pH to 3.0, and stirring at room temperature for 30min to obtain a solution b; dissolving 20 parts by weight of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in 35 parts by weight of absolute ethyl alcohol to obtain a solution c;
and S2, adding the solution b into the dispersion liquid a under the nitrogen condition, continuously stirring at the rotating speed of 350rpm, simultaneously heating to 60 ℃ and keeping for 2 hours, then adding the solution c, heating to 90 ℃ and keeping for 4 hours, centrifuging after the reaction is finished, taking the bottom precipitate, washing, and freeze-drying to obtain the modified magnesium hydroxide.
A preparation method of flame-retardant chloroprene rubber comprises the following steps:
(1) the chloroprene rubber and the trans-1, 4-butadiene-isoprene copolymer rubber are put into an internal mixer, roll-coating plastication is carried out for 15min, then the anti-aging agent, the stearic acid, the white carbon black, the flame retardant, the accelerator and the zinc oxide are sequentially added, and rubber tapping is carried out after mixing for 30min, so as to obtain rubber compound;
(2) and (3) vulcanizing the rubber compound obtained in the step (1) on a flat vulcanizing machine to obtain the flame-retardant chloroprene rubber.
The vulcanization conditions are as follows: the temperature is 165 ℃, the pressure is 15MPa, and the time is 15 min.
Example 3
The flame-retardant chloroprene rubber is prepared from the following raw materials: 80 parts of chloroprene rubber, 20 parts of trans-1, 4-butadiene-isoprene copolymer rubber, 2 parts of accelerator, 1.5 parts of anti-aging agent, 1.5 parts of stearic acid, 25 parts of white carbon black, 8 parts of zinc oxide and 10 parts of flame retardant.
The accelerator is an accelerator MTT-80.
The anti-aging agent is an anti-aging agent 4020.
The flame retardant is functionalized magnesium hydroxide.
The preparation method of the functionalized magnesium hydroxide comprises the following steps:
s1, dispersing 30 parts by weight of magnesium hydroxide in 100 parts by weight of absolute ethyl alcohol to obtain a dispersion liquid a; adding 1 part by weight of gamma- (2, 3-epoxypropane) propyl trimethoxy silane into a mixed solution consisting of 15 parts by weight of water and 100 parts by weight of absolute ethyl alcohol, adjusting the pH to 3.0, and stirring at room temperature for 30min to obtain a solution b; dissolving 20 parts by weight of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in 35 parts by weight of absolute ethyl alcohol to obtain a solution c;
s2, adding the solution b into the dispersion liquid a under the nitrogen condition, continuously stirring at the rotating speed of 350rpm, simultaneously heating to 60 ℃ and keeping for 2 hours, then adding the solution c, heating to 90 ℃ and keeping for 4 hours, centrifuging after the reaction is finished, taking the bottom precipitate, washing, and freeze-drying to obtain modified magnesium hydroxide;
s3, uniformly mixing 12.5 parts by weight of melamine, 20 parts by weight of formaldehyde, 20 parts by weight of n-butanol and 20 parts by weight of water, adjusting the pH to 8.5, and stirring at the rotating speed of 800rpm at 70 ℃ for 30min to obtain a melamine formaldehyde resin prepolymer solution;
s4, adding the whole melamine formaldehyde resin prepolymer solution obtained in the step S3, 1 part by weight of sodium dodecyl sulfate and 40 parts by weight of modified magnesium hydroxide obtained in the step S2 into 100 parts by weight of water, stirring at the rotating speed of 500rpm at 60 ℃ for 60min, cooling to room temperature, adjusting the pH to 9.0, continuing to stir for 30min, filtering, washing and drying to obtain the functionalized magnesium hydroxide.
A preparation method of flame-retardant chloroprene rubber comprises the following steps:
(1) the chloroprene rubber and the trans-1, 4-butadiene-isoprene copolymer rubber are put into an internal mixer, roll-coating plastication is carried out for 15min, then the anti-aging agent, the stearic acid, the white carbon black, the flame retardant, the accelerator and the zinc oxide are sequentially added, and rubber tapping is carried out after mixing for 30min, so as to obtain rubber compound;
(2) and (3) vulcanizing the rubber compound obtained in the step (1) on a flat vulcanizing machine to obtain the flame-retardant chloroprene rubber.
The vulcanization conditions are as follows: the temperature is 165 ℃, the pressure is 15MPa, and the time is 15 min.
Example 4
The flame-retardant chloroprene rubber is prepared from the following raw materials: 80 parts of chloroprene rubber, 20 parts of trans-1, 4-butadiene-isoprene copolymer rubber, 2 parts of accelerator, 1.5 parts of anti-aging agent, 1.5 parts of stearic acid, 25 parts of white carbon black, 8 parts of zinc oxide and 10 parts of flame retardant.
The accelerator is an accelerator MTT-80.
The anti-aging agent is an anti-aging agent 4020.
The flame retardant is functionalized magnesium hydroxide.
The preparation method of the functionalized magnesium hydroxide comprises the following steps:
s1, dispersing 30 parts by weight of magnesium hydroxide in 100 parts by weight of absolute ethyl alcohol to obtain a dispersion liquid a; adding 1 part by weight of gamma- (2, 3-epoxypropane) propyl trimethoxy silane into a mixed solution consisting of 15 parts by weight of water and 100 parts by weight of absolute ethyl alcohol, adjusting the pH to 3.0, and stirring at room temperature for 30min to obtain a solution b; dissolving 20 parts by weight of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in 35 parts by weight of absolute ethyl alcohol to obtain a solution c;
s2, under the condition of nitrogen, adding the solution b into the dispersion liquid a, continuously stirring at the rotating speed of 350rpm, simultaneously heating to 60 ℃ and keeping for 2 hours, then adding the solution c, heating to 90 ℃ and keeping for 4 hours, centrifuging after the reaction is finished, taking the bottom precipitate, washing, and freeze-drying to obtain modified magnesium hydroxide;
s3, uniformly mixing 12.5 parts by weight of melamine, 20 parts by weight of formaldehyde, 20 parts by weight of n-butanol and 20 parts by weight of water, adjusting the pH to 8.5, and stirring at the rotating speed of 800rpm at 70 ℃ for 30min to obtain a melamine formaldehyde resin prepolymer solution;
s4, adding the whole melamine formaldehyde resin prepolymer solution obtained in the step S3, 1 part by weight of polyoxyethylene octylphenol ether and 40 parts by weight of modified magnesium hydroxide obtained in the step S2 into 100 parts by weight of water, stirring at the rotation speed of 500rpm at 60 ℃ for 60min, cooling to room temperature, adjusting the pH to 9.0, continuing to stir for 30min, filtering, washing and drying to obtain the functionalized magnesium hydroxide.
A preparation method of flame-retardant chloroprene rubber comprises the following steps:
(1) the chloroprene rubber and the trans-1, 4-butadiene-isoprene copolymer rubber are put into an internal mixer, roll-coating plastication is carried out for 15min, then the anti-aging agent, the stearic acid, the white carbon black, the flame retardant, the accelerator and the zinc oxide are sequentially added, and rubber tapping is carried out after mixing for 30min, so as to obtain rubber compound;
(2) and (3) vulcanizing the rubber compound obtained in the step (1) on a flat vulcanizing machine to obtain the flame-retardant chloroprene rubber.
The vulcanization conditions are as follows: the temperature is 165 ℃, the pressure is 15MPa, and the time is 15 min.
Example 5
The flame-retardant chloroprene rubber consists of the following raw materials: 80 parts of chloroprene rubber, 20 parts of trans-1, 4-butadiene-isoprene copolymer rubber, 2 parts of accelerator, 1.5 parts of anti-aging agent, 1.5 parts of stearic acid, 25 parts of white carbon black, 8 parts of zinc oxide and 10 parts of flame retardant.
The accelerator is an accelerator MTT-80.
The anti-aging agent is an anti-aging agent 4020.
The flame retardant is functionalized magnesium hydroxide.
The preparation method of the functionalized magnesium hydroxide comprises the following steps:
s1, dispersing 30 parts by weight of magnesium hydroxide in 100 parts by weight of absolute ethyl alcohol to obtain a dispersion liquid a; adding 1 part by weight of gamma- (2, 3-epoxypropane) propyl trimethoxy silane into a mixed solution consisting of 15 parts by weight of water and 100 parts by weight of absolute ethyl alcohol, adjusting the pH to 3.0, and stirring at room temperature for 30min to obtain a solution b; dissolving 20 parts by weight of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in 35 parts by weight of absolute ethyl alcohol to obtain a solution c;
s2, adding the solution b into the dispersion liquid a under the nitrogen condition, continuously stirring at the rotating speed of 350rpm, simultaneously heating to 60 ℃ and keeping for 2 hours, then adding the solution c, heating to 90 ℃ and keeping for 4 hours, centrifuging after the reaction is finished, taking the bottom precipitate, washing, and freeze-drying to obtain modified magnesium hydroxide;
s3, uniformly mixing 12.5 parts by weight of melamine, 20 parts by weight of formaldehyde, 20 parts by weight of n-butanol and 20 parts by weight of water, adjusting the pH to 8.5, and stirring at the rotating speed of 800rpm at 70 ℃ for 30min to obtain a melamine formaldehyde resin prepolymer solution;
s4, adding the whole melamine formaldehyde resin prepolymer solution obtained in the step S3, 1 part by weight of dispersing agent and 40 parts by weight of modified magnesium hydroxide obtained in the step S2 into 100 parts by weight of water, stirring at the rotating speed of 500rpm at 60 ℃ for 60min, cooling to room temperature, adjusting the pH to 9.0, continuing to stir for 30min, filtering, washing and drying to obtain the functionalized magnesium hydroxide.
The dispersing agent is a mixture of sodium dodecyl sulfate and polyoxyethylene octyl phenol ether, wherein the mass ratio of the sodium dodecyl sulfate to the polyoxyethylene octyl phenol ether is 3: 1.
A preparation method of flame-retardant chloroprene rubber comprises the following steps:
(1) the chloroprene rubber and the trans-1, 4-butadiene-isoprene copolymer rubber are put into an internal mixer, roll-coating plastication is carried out for 15min, then the anti-aging agent, the stearic acid, the white carbon black, the flame retardant, the accelerator and the zinc oxide are sequentially added, and rubber tapping is carried out after mixing for 30min, so as to obtain rubber compound;
(2) and (3) vulcanizing the rubber compound obtained in the step (1) on a flat vulcanizing machine to obtain the flame-retardant chloroprene rubber.
The vulcanization conditions are as follows: the temperature is 165 ℃, the pressure is 15MPa, and the time is 15 min.
Test example 1
And (3) evaluating the flame retardant property:
the oxygen index is tested according to GB/T10707-.
γLOI=qV（O2）/[qV（O2）+qV（N2）]×100%
Wherein qv (O)2) And qv (N)2) Respectively represents the volume flow of oxygen and the volume flow of nitrogen, and the unit is L.min-1；γLOIRepresents the oxygen index. The larger the oxygen index, the better the flame retardant performance.
Each group of samples was tested in parallel five times and the test results were averaged.
TABLE 1 flame retardancy test results
| γLOI(%) | |
| Example 1 | 33.4 |
| Example 2 | 39.6 |
| Example 3 | 47.8 |
| Example 4 | 48.0 |
| Example 5 | 51.3 |
From the above results, it can be seen that the flame retardant performance of example 2 is better than that of example 1, and it is mainly possible that after magnesium hydroxide is modified by 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the modified magnesium hydroxide obtained has a cyclic diphenyl phosphate group, can act synergistically with magnesium hydroxide, and has excellent gas-phase high-efficiency flame retardant performance. Compared with the example 2, the flame retardant performance of the examples 3 to 5 is obviously improved, probably because the environmental-friendly nitrogen-based flame retardant melamine formaldehyde resin is adsorbed on the surface of the modified magnesium hydroxide by a sol-gel method, so that a shell is formed on the surface of the modified magnesium hydroxide, and the functionalized magnesium hydroxide with a core @ double-shell structure is obtained, and the performance of the functionalized magnesium hydroxide is better than that of the modified magnesium hydroxide, probably because: 1) the P-C bond in the functionalized magnesium hydroxide is broken to generate an acidic substance, and particularly at high temperature, such as phosphoric acid and polyphosphoric acid, vermicular carbon can be combined together, so that the gaps among carbon layers are reduced, and a compact, continuous and expanded carbon layer is formed; 2) the endothermic decomposition of magnesium hydroxide in the functionalized magnesium hydroxide releases high-temperature water vapor, can dilute hot air and cool the surface of a pyrolysis area, and generates a magnesium oxide carbon residue layer with a physical protection function; 3) the decomposition of melamine formaldehyde resin in functionalized magnesium hydroxide releases non-combustible gases (e.g., NO) during combustionx) Thereby diluting the combustible gas and oxygen concentration surrounding the material. Therefore, the functionalized magnesium hydroxide prepared by the invention is used as a flame retardant to be doped with chlorineBetter synergistic flame-retardant effect can be shown in the butadiene rubber, and the flame-retardant property of the chloroprene rubber is improved.
Compared with the embodiment 3 or 4, the embodiment 5 has better flame retardant performance, probably because the lauryl sodium sulfate and the polyoxyethylene octyl phenol ether are adopted as the dispersing agent together in the embodiment 5, the lauryl sodium sulfate can be adsorbed on the surface of the modified magnesium hydroxide solid, the wettability of the modified magnesium hydroxide solid is improved, the dispersion condition of the modified magnesium hydroxide solid is improved, the particle size of the microsphere is reduced, and the particle size distribution is more uniform; and the polyoxyethylene octyl phenol ether has a charge effect which can keep and control fine resin particles precipitated from a continuous phase to be uniformly precipitated on the surface of the modified magnesium hydroxide to form a capsule wall, and regulate and control the polymerization reaction of the melamine formaldehyde resin. The two components act together to promote the prepared functionalized magnesium hydroxide microcapsule to have no adhesion phenomenon, have good compactness and complete sphere and are beneficial to further improving the flame retardant property.
Test example 2
Evaluation of mechanical properties:
the tensile property is tested by reference to national standard GB/T528-. Test temperature: 25 ℃, stretching rate: 500 mm/min. Each group of samples was tested in parallel five times and the test results were averaged.
TABLE 2 mechanical Property test results
| Tensile strength, MPa | Elongation at break,% | |
| Example 1 | 14.8 | 575 |
| Example 2 | 17.6 | 657 |
| Example 5 | 21.2 | 753 |
The results show that the functionalized magnesium hydroxide prepared by the invention is used as the flame retardant of the chloroprene rubber, so that the problem of reduction of mechanical properties caused by the adoption of magnesium hydroxide as the flame retardant in the prior art is effectively solved, the functionalized magnesium hydroxide mainly has a unique core @ double-shell structure, the surface of the functionalized magnesium hydroxide is rough, the dispersibility of the functionalized magnesium hydroxide is good, and the melamine formaldehyde resin on the outer layer can form a cross-linking network in a matrix, so that the binding force between the functionalized magnesium hydroxide and the matrix is strong, the physical cross-linking points of the chloroprene rubber matrix are increased, the cross-linking density is increased, the macromolecular chain motion of the chloroprene rubber is limited, the capability of the chloroprene rubber for inhibiting crack propagation is improved, and the mechanical properties of the flame-retardant chloroprene rubber are improved.
Claims (9)
1. The flame-retardant chloroprene rubber is characterized by comprising the following raw materials: chloroprene rubber, trans-1, 4-butadiene-isoprene copolymer rubber, an accelerator, an anti-aging agent, stearic acid, white carbon black, zinc oxide and a flame retardant.
2. The flame-retardant chloroprene rubber according to claim 1, wherein the flame retardant is any one of magnesium hydroxide, modified magnesium hydroxide and functionalized magnesium hydroxide.
3. The flame retardant chloroprene rubber according to claim 2, wherein the modified magnesium hydroxide is prepared by the following steps:
s1, dispersing 25-40 parts by weight of magnesium hydroxide in 90-110 parts by weight of absolute ethyl alcohol to obtain a dispersion liquid a; adding 0.5-2 parts by weight of silane coupling agent into a mixed solution consisting of 10-20 parts by weight of water and 90-110 parts by weight of absolute ethyl alcohol, adjusting the pH to 2.5-4, and stirring at room temperature for 20-40min to obtain a solution b; dissolving 15-30 parts by weight of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in 30-40 parts by weight of absolute ethyl alcohol to obtain a solution c;
and S2, adding the solution b into the dispersion liquid a under the nitrogen condition, stirring while heating to 50-70 ℃ and keeping for 1-3h, then adding the solution c, heating to 80-95 ℃ and keeping for 3-5h, centrifuging after the reaction is finished, taking the bottom precipitate, washing, and freeze-drying to obtain the modified magnesium hydroxide.
4. The flame retardant chloroprene rubber according to claim 2, wherein the functionalized magnesium hydroxide is prepared by the following steps:
s1, dispersing 25-40 parts by weight of magnesium hydroxide in 90-110 parts by weight of absolute ethyl alcohol to obtain a dispersion liquid a; adding 0.5-2 parts by weight of silane coupling agent into a mixed solution consisting of 10-20 parts by weight of water and 90-110 parts by weight of absolute ethyl alcohol, adjusting the pH to 2.5-4, and stirring at room temperature for 20-40min to obtain a solution b; dissolving 15-30 parts by weight of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in 30-40 parts by weight of absolute ethyl alcohol to obtain a solution c;
s2, adding the solution b into the dispersion liquid a under the nitrogen condition, stirring while heating to 50-70 ℃ and keeping for 1-3h, then adding the solution c, heating to 80-95 ℃ and keeping for 3-5h, centrifuging after the reaction is finished, taking the bottom precipitate, washing, and freeze-drying to obtain modified magnesium hydroxide;
s3, uniformly mixing 10-15 parts by weight of melamine, 15-25 parts by weight of formaldehyde, 15-25 parts by weight of n-butanol and 15-25 parts by weight of water, adjusting the pH to 8-9, and stirring at 65-80 ℃ for 20-40min to obtain a melamine-formaldehyde resin prepolymer solution;
s4, adding the whole melamine formaldehyde resin prepolymer solution obtained in the step S3, 0.5-2 parts by weight of dispersant and 30-45 parts by weight of modified magnesium hydroxide obtained in the step S2 into 80-120 parts by weight of water, stirring at 55-65 ℃ for 50-80min, cooling to room temperature, adjusting the pH to 8-10, continuing to stir for 20-40min, filtering, washing and drying to obtain the functionalized magnesium hydroxide.
5. The flame-retardant chloroprene rubber according to claim 3 or 4, wherein the silane coupling agent is any one of vinyltriethoxysilane and gamma- (2, 3-epoxypropane) propyltrimethoxysilane divinyltriaminopropyltrimethoxysilane.
6. The flame-retardant chloroprene rubber according to claim 4, wherein the dispersant is sodium lauryl sulfate and/or polyoxyethylene octylphenol ether.
7. The flame-retardant chloroprene rubber according to claim 1, wherein the accelerator is any one of an accelerator NA-22, an accelerator MTT-80 and an accelerator TMTD.
8. The flame-retardant chloroprene rubber according to claim 1, wherein the antioxidant is any one of an antioxidant 4020, an antioxidant RD and an antioxidant ODA.
9. A process for the preparation of the flame retardant neoprene according to any one of claims 1-8 comprising the steps of:
(1) the chloroprene rubber and the trans-1, 4-butadiene-isoprene copolymer rubber are put into an internal mixer, roll-coated plasticating is carried out, then the anti-aging agent, the stearic acid, the white carbon black, the flame retardant, the accelerator and the zinc oxide are sequentially added, and rubber is produced after mixing to obtain mixed rubber;
(2) and (3) vulcanizing the rubber compound obtained in the step (1) on a flat vulcanizing machine to obtain the flame-retardant chloroprene rubber.
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| CN117265689A (en) * | 2023-10-16 | 2023-12-22 | 浙江汇隆新材料股份有限公司 | Regenerated colored flame-retardant fiber and preparation method thereof |
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