CN107540896B - Preparation method of easily-processed flame-retardant nitrile rubber - Google Patents
Preparation method of easily-processed flame-retardant nitrile rubber Download PDFInfo
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Abstract
The invention provides a method for easily processing flame-retardant nitrile rubber, which comprises the steps of firstly dissolving nitrile rubber in a solvent to prepare a solution, adding an olefin metathesis catalyst and a rubber flame retardant, and removing a glue solution after reaction through the solvent to obtain a flame-retardant plasticizer; dispersing the plasticizer into water under the action of an emulsifier to form emulsion, mixing the emulsion with butyronitrile latex, and then coagulating, washing and drying to obtain the flame-retardant nitrile rubber product easy to process. The plasticizer product can reduce Mooney 0.7 unit/part of base rubber and improve oxygen index by 0.2 percent/part.
Description
Technical Field
The invention relates to a preparation method of nitrile rubber, in particular to a preparation method of flame-retardant nitrile rubber which is easy to process.
Background
The flame retardant method in the rubber field mainly comprises two methods of adding a flame retardant and blending with flame retardant rubber. The flame retardant is added with inorganic flame retardant and organic flame retardant, the inorganic flame retardant generally has cooling and blocking effects, and common varieties comprise aluminum hydroxide, magnesium hydroxide, boron series substances, molybdenum series substances and the like; the organic flame retardant is mainly bromine, chlorine or phosphorus-containing organic compounds, and bromine flame retardant can release hydrogen bromide during combustion to play a role in blocking oxygen. It was proposed by Zhi et al in "flame retardant rubber shallow analysis" (world rubber industry, vol. 31, No. 4, p.39) to add 15 parts of Sb to SBR2O3And 30 parts of chlorinated paraffin or 5 parts of Sb2O320 parts of chlorinated paraffin and 25 parts of Al (OH)3And the rubber material with better flame retardance can be obtained. Liang et al, in "flame retardant for rubber and flame retardant" (Special rubber products, vol.23, No. 3, page 25), proposed to mix bromine-containing phosphate, aromatic bromide, Sb2O3And 4 flame retardants of ammonium chloride are used together and added into SBR to obtain a sizing material with good flame retardant effect. Using 5-10 parts of dialkyl phenyl phosphate and 10-15 parts of Sb2O3And 3-10 parts of iodine are added into the SBR to obtain the sizing material with good flame retardant effect. The flame-retardant rubber is mainly a rubber species containing halogen, such as chloroprene rubber, polyvinyl chloride, epichlorohydrin rubber, chlorosulfonated polyethylene and the like.
The inorganic flame retardant has the defects of large useful amount and high cost, even if the factors are not considered, the additional flame retardant is not easy to realize in the production process of rubber, the self-agglomeration of the inorganic powder is serious, and the mixing of the inorganic powder and the rubber needs high energy, so that the repeated kneading and mixing for a long time on an open mill or an internal mixer are generally required. In the open milling or banburying process, a certain amount of plasticizer is generally required to be added. Generally, the low molecular weight substances can provide a certain flexibility to the rubber compound, and can increase the plasticity, fluidity and adhesiveness of the rubber compound so as to facilitate the technological operations such as compression, molding and the like. And the dispersion of the powdery compounding agent is facilitated, the mixing temperature is reduced, and the processability of the rubber is improved.
Nitrile rubber has better oil resistance due to the polar action of nitrile groups, is commonly used in the fields of rubber tubes, adhesive tapes, sealing materials and the like, and most petroleum plasticizers are used in rubber processing, mainly comprise aromatic oil, paraffin oil, naphthenic oil, heavy oil, paraffin, vaseline, asphalt, petroleum resin and the like, and are not suitable for nitrile rubber processing systems. The nitrile rubber is generally plasticizer by esters such as di-2-ethylhexyl phthalate. CN 200310108748.5A dibasic acid ester plasticizer and its manufacturing method, its characteristic is, it is by adipic acid and ether alcohol under 115 ~ 125 duC and 84 ~ 97KPa vacuum decompression condition, through esterification reaction. The plasticizer has the characteristics of good compatibility, small volatilization loss and difficult extraction and washing, has obvious effect on improving the low-temperature flexibility of the polymer material, and does not sacrifice the performance of the material. It is particularly suitable for polar rubbers such as nitrile rubber, acrylate rubber, epichlorohydrin rubber and the like, but also for vinyl resins, cellulose resins and the like. CN97181179.2 polyurethane prepolymers with a low monomer content, polyurethane prepolymers with a low monomer content containing free NCO groups, prepared from polyhydroxyl alcohols and diisocyanates of different reactivity, characterized by the ratio of the NCO groups of the diisocyanates which react relatively slowly to the NCO groups of the diisocyanates which react rapidly. The prepolymer is prepared by a two-stage reaction. The prepolymers of the invention are useful for bonding plastic articles, metals and paper, especially film materials. The plasticizers reported in the patent are mostly ester plasticizers, have good compatibility with nitrile rubber, have good softening effect, but have no flame retardant effect, and are easy to separate out in the using process of products.
Disclosure of Invention
The invention aims to provide a preparation method of easily processed flame-retardant nitrile rubber, and particularly relates to a method for preparing easily processed flame-retardant rubber products by adding a plasticizer with a flame-retardant function into nitrile rubber latex and performing a liquid-phase mixing process.
The preparation method of the easily-processed flame-retardant nitrile rubber comprises the following specific steps:
1) firstly, preparing a flame-retardant plasticizer, dissolving nitrile rubber in a solvent to prepare a solution with 0.1-20% w, preferably 1-15% w, adding 0.5-1.5 parts, preferably 0.8-1.2 parts of olefin double decomposition catalyst and 10-60 parts, preferably 15-35 parts of rubber flame retardant based on 100 parts by mass of rubber, isolating air and water at 15-50 ℃, preferably 20-25 ℃, reacting for 0.5-5 hours, preferably 1-2 hours, and removing the reacted glue solution through the solvent to obtain a flame-retardant plasticizer product with Mn of 200-8000;
2) adding the prepared flame-retardant plasticizer product, an emulsifier and water, mixing, and stirring to prepare a plasticizer emulsion;
3) adding latex and flame-retardant plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: (1 to 50), preferably 100: (10-40), mixing to prepare mixed latex, adding 1-25 parts by mass of coagulant at the reaction temperature of 10-80 ℃ for coagulation, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
Tests show that the easy-to-process flame-retardant nitrile rubber prepared by the invention reduces the Mooney property of the base rubber by 0.7 unit/part and improves the oxygen index by 0.2 percent/part.
The solvent is a solvent which does not contain alkene in the structure and can dissolve the nitrile rubber; selected from chloroform, chlorobenzene, acetone, butanone, etc.
The rubber flame retardant is an organic chloride monomer containing an alkene unsaturated substituent, and the structural formula of the organic chloride monomer is as follows: RX; wherein: r-an unsaturated olefin aliphatic chain segment containing 2-18 carbon atoms, which can be vinyl, propenyl, isopropenyl, isopentenyl, 3-pentenyl, 6-octenyl, tetramethylvinyl, 1-heptenyl, methacryloxypropyl, methacryloxy, preferably vinyl; x is F, Cl, Br, or I, preferably Br;
r in RX preferably contains a nitrile group, so that the R is convenient to dissolve in a polar solvent, the compatibility with nitrile rubber is improved, and the reaction activity is enhanced;
the rubber flame retardant can be vinyl chloride, chlorinated acrylonitrile, brominated acrylonitrile, vinyl bromide, dichloroethylene, ethylene dibromide, isomers thereof and the like;
the olefin metathesis catalyst of the invention is a ruthenium carbene complex catalyst, which can be (o-isopropoxybenzylidene) (tricyclohexylphosphine) ruthenium (II) dichloride
Dichloro [ o-isopropoxybenzylidene ] group][1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolinylidene]Ruthenium complex
Etc. of Grubbs series catalysts having similar functions or other metal carbene catalysts having olefin metathesis function, preferably
Or
The invention does not specially limit the types and the dosage of the emulsifier and the coagulant, and can adopt the commonly used auxiliary agents and dosage in the field. The emulsifier can be saturated or unsaturated fatty acid soap, rosin acid soap and other anionic emulsifiers; the amount of the flame retardant plasticizer can be 0.1-20 parts, preferably 0.5-10 parts, added to 100 parts of flame retardant plasticizer product.
The addition amount of water in the preparation process of the plasticizer emulsion is not particularly required, as long as the materials can form an emulsion state, and the addition amount of water is preferably 50-500 parts by weight of water added into 100 parts of flame-retardant plasticizer products.
The temperature of the plasticizer emulsion preparation process is not particularly limited in the present invention, as long as the emulsion can be formed under stirring, and for example, the temperature may be preferably 10 to 80 ℃.
The coagulant of the invention can be CaCl2、MgSO4、Mg Cl2、Al2SO4、FeCl3、CuCl2、Ca(HSO4)2And soluble metal salts and mixtures thereof. The amount of the coagulant is preferably 1 to 25 parts by mass, preferably 5 to 15 parts by mass, based on 100 parts of the nitrile latex.
The term "part" as used herein means a part by mass.
The invention is based on the technical principle that:
n is more than m in the formula (1)
As shown in the chemical reaction formula (1), the molecular weight of the nitrile rubber is reduced under the action of an olefin metathesis catalyst, and a halogen flame-retardant group is introduced into a side group; the introduction of monomolecular olefin in the reaction process accelerates the degradation reaction, and functional groups can be introduced into side groups and end groups; if no monomolecular olefin is added, the double decomposition reaction process is slow, and side reactions such as cross-linking between side groups are intensified; rubber combustion in the presence of oxygen is a very vigorous oxidation reaction, also a chain chemical reaction, which generates reactive HO-radicals when burned, and hydrocarbons and water when the HO-radicals encounter rubber molecules. Under aerobic conditions, the hydrocarbon can continue to decompose and generate HO-free radicals, thereby forming chain reactions and continuing the combustion. To prevent burning or to extinguish the rubber, it is necessary to block oxygen or to reduce the concentration of HO-radicals. The flame-retardant plasticizer is heated and decomposed to release halogen gas and hydrogen halide, and the halogen can play a certain role in blocking oxygen; the hydrogen halide can react with HO-free radicals to generate water and halogen ions, the halogen ions can react with hydrocarbons to generate hydrogen halide, and the hydrogen halide can further eliminate the HO-free radicals, thereby reducing the concentration of the HO-free radicals and slowing the combustion speed until the HO-free radicals are extinguished. Meanwhile, the plasticizer is generated after the nitrile rubber is degraded, has the same composition with the rubber base material, plays a role in softening in the rubber processing process, and is vulcanized and crosslinked with the base material in the later vulcanization process.
Detailed Description
The raw material auxiliaries required for the specific implementation of the invention are as follows:
(1) nitrile butadiene rubbers NBR3305, NBR2907, technical grade, Lanzhou petrochemical division;
(2) vinyl chloride, chlorinated acrylonitrile, brominated acrylonitrile, 1-dichloroethylene, bromoethylene, trans-1, 2-dibromoethylene, reagent grade, carbofuran technologies ltd;
(3) olefin metathesis catalyst:
and
ruthenium carbene catalyst, 500 mg/bottle, purity more than or equal to 98% w, Bailingwei science and technology Limited;
(4) chloroform, chlorobenzene, acetone, butanone, reagent grade, carbofuran technologies ltd;
(5) sodium aliphatate, sodium abietate, potassium aliphatate, potassium abietate, technical grade, Lanzhou petrochemical division;
(6)CaCl2、MgSO4、MgCl2、Al2(SO4)3industrial grade, langzhou petrochemical division;
blending a plasticizer with the nitrile rubber on an open mill, and testing the Mooney viscosity and the oxygen index of the raw rubber; the Mooney viscosity of the rubber is measured according to GB/T1232.1-2000, and the molecular weight of the rubber plasticizer is measured by GPC. The oxygen index is tested according to GB 10707-89, the high oxygen index indicates that the material is not easy to burn, the low oxygen index indicates that the material is easy to burn, the oxygen index is less than 22 and belongs to flammable materials, the oxygen index is between 22 and 27 and belongs to the nonflammable materials, and the oxygen index is more than 27.
The parts are all parts by mass; the "%" is calculated by mass percent, and is calculated according to 100 rubber dry basis mass without special indication.
Example 1:
nitrile rubber NBR3305 was dissolved in chloroform to prepare a 0.15% solution, and 1.3 parts by mass of an olefin metathesis catalyst was added to 100 parts by mass of the rubber
And 11.9 parts of rubber flame retardant chlorinated acrylonitrile, isolating air and water at 15.5 ℃, reacting for 0.53 hour, and removing the reacted glue solution through a solvent to obtain a flame-retardant plasticizer product with Mn of 5500;
adding 100g of the prepared flame-retardant plasticizer product, 0.15g of emulsifier sodium fatty acid and 55g of desalted water into an emulsifier, controlling the temperature to be 75 ℃, and stirring to prepare a plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: 10 are mixed to prepare mixed latex, 20 parts by mass of coagulant CaCl is added at the reaction temperature of 78 DEG C2Coagulating, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
The Mooney viscosity is reduced from 55 to 45 and the oxygen index is increased from 19.7 to 25.9 percent.
Comparative example 1:
compared with the example 1, the other conditions are the same, except that no flame retardant is added, specifically: nitrile rubber NBR3305 was dissolved in chloroform to prepare a 0.15% solution, and 1.3 parts by mass of an olefin metathesis catalyst was added to 100 parts by mass of the rubber
Air and water are isolated at 15.5 ℃, the reaction is carried out for 0.53 hour, and the glue solution after the reaction is removed through a solvent, so that the flame-retardant plasticizer product with Mn of 10800 is obtained;
adding 100g of the prepared flame-retardant plasticizer product, 0.15g of emulsifier sodium fatty acid and 55g of desalted water into an emulsifier, controlling the temperature to be 75 ℃, and stirring to prepare a plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: 10 are mixed to prepare mixed latex, 20 parts by mass of coagulant CaCl is added at the reaction temperature of 78 DEG C2Coagulating, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
The Mooney viscosity was tested to decrease from 55 to 53 and the oxygen index was 19.7% without increasing.
Example 2:
nitrile butadiene rubber NBR3305 is dissolved in acetone solvent to prepare 10% solution, and 0.98 parts of olefin metathesis catalyst is added based on 100 parts by mass of rubber
And 48 parts of rubber flame retardant 1, 1-dichloroethylene, the air and the water are isolated at 48.9 ℃, the reaction is carried out for 4.5 hours, and the glue solution after the reaction is removed by a solvent, so as to obtain a flame-retardant plasticizer product with Mn of 3200;
adding 100g of the prepared flame-retardant plasticizer product, 19g of emulsifier sodium fatty acid and 490g of desalted water into an emulsifier, controlling the temperature to be 50 ℃, and stirring to prepare a plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: 30 are mixed to prepare mixed latex, 20 parts by mass of coagulant MgSO is added at the reaction temperature of 55 DEG C4Coagulating, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
The Mooney viscosity is reduced from 55 to 32 and the oxygen index is increased from 19.7% to 27.2% through tests.
Comparative example 2:
compared with example 2, the other conditions are the same, except that no olefin metathesis catalyst is added, specifically: dissolving nitrile butadiene rubber NBR3305 in an acetone solvent to prepare a 10% w solution, adding 48 parts by mass of rubber flame retardant 1, 1-dichloroethylene based on 100 parts by mass of rubber, isolating air and water at 48.9 ℃, reacting for 4.5 hours, and removing a glue solution after reaction through the solvent to obtain a flame-retardant plasticizer product with Mn of 175000;
adding 100g of the prepared flame-retardant plasticizer product, 19g of emulsifier sodium fatty acid and 490g of desalted water into an emulsifier, controlling the temperature to be 50 ℃, and stirring to prepare a plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: 30 are mixed to prepare mixed latex, 20 parts by mass of coagulant MgSO is added at the reaction temperature of 55 DEG C4Coagulating, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
The test shows that the Mooney viscosity is 55 without reduction, the oxygen index is increased from 19.7% to 20.4%, and white smoke generated by decomposing 1, 1-dichloroethylene exists during coagulation and drying.
Example 3:
nitrile rubber NBR2907 is dissolved in chlorobenzene solvent to prepare 2.51% solution, and 1.41 parts of olefin metathesis catalyst is added based on 100 parts of rubber by mass
And 25.2 parts of rubber flame retardant vinyl bromide, isolating air and water at 25.5 ℃, reacting for 2.55 hours, and removing a glue solution after the reaction through a solvent to obtain a flame-retardant plasticizer product with Mn of 520;
adding 100g of the prepared flame-retardant plasticizer product, 10g of emulsifier sodium abietate and 250g of desalted water into an emulsifier, controlling the temperature to be 40 ℃, and stirring to prepare a plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: 25 to prepare a mixed latex, and adding 20 parts by mass of a coagulant MgSO into the mixed latex at a reaction temperature of 55 DEG C4Coagulating, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
The Mooney viscosity is reduced from 75 to 55 and the oxygen index is increased from 19.7% to 25.8%.
Comparative example 3:
the same conditions as in example 3 were followed, except that di-2-ethylhexyl phthalate was used as plasticizer, specifically: adding 100g of the plasticizer, 10g of sodium abietate emulsifier and 250g of desalted water into an emulsifier, controlling the temperature to be 40 ℃, and stirring to prepare a plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulating kettle according to a dry basis ratio of 100: 25 to prepare a mixed latex, and adding 20 parts by mass of a coagulant MgSO into the mixed latex at a reaction temperature of 55 DEG C4Coagulating, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
The Mooney viscosity was tested to be reduced from 75 to 53 and the oxygen index was reduced from 19.7% to 16.8%, which is more flammable.
Example 4:
nitrile rubber NBR2907 is dissolved in butanone solvent to prepare 4.5% solution, and 0.59 parts of olefin metathesis catalyst is added based on 100 parts of rubber by mass
And 13 parts of rubber flame retardant vinyl bromide, isolating air and water at 15 ℃, reacting for 4.9 hours, and removing the reacted glue solution through a solvent to obtain a flame-retardant plasticizer product with Mn of 7300;
adding 100g of the prepared flame-retardant plasticizer product, 18g of emulsifier potassium abietate and 450g of desalted water into an emulsifier, controlling the temperature to be 60 ℃, and stirring to prepare a plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: 40 are mixed to prepare mixed latex, and 15 parts by mass of coagulant Al is added at the reaction temperature of 30 DEG C2(SO4)3Coagulating, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
The Mooney viscosity is reduced to 41 from 75 and the oxygen index is increased to 28.6 from 19.7 percent.
Comparative example 4:
the other conditions were the same as in example 4, except that 1, 1-dibromoethane, which is a flame retardant, was used, and there were no double bonds, specifically: dissolving nitrile-butadiene rubber NBR2907 inA4.5% solution was prepared in a methyl ethyl ketone solvent, and 0.59 part by mass of an olefin metathesis catalyst was added to 100 parts by mass of a rubber
And 13 parts of rubber flame retardant 1, 1-dibromoethane, the mixture is isolated from air and water at 15 ℃, the reaction is carried out for 4.9 hours, and the glue solution after the reaction is removed by a solvent to obtain a flame-retardant plasticizer product with Mn of 38000;
adding 100g of the prepared flame-retardant plasticizer product, 18g of emulsifier potassium abietate and 450g of desalted water into an emulsifier, controlling the temperature to be 60 ℃, and stirring to prepare a plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: 40 are mixed to prepare mixed latex, and 15 parts by mass of coagulant Al is added at the reaction temperature of 30 DEG C2(SO4)3Coagulating, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
Tests show that the Mooney viscosity is reduced to 69 from 75, the oxygen index is increased to 20.4 from 19.7%, and white smoke generated by decomposing 1, 1-dibromoethane exists during condensation and drying.
Example 5:
nitrile rubber NBR3305 was dissolved in chloroform to prepare a 3.75% solution, and 0.85 part by mass of an olefin metathesis catalyst was added to 100 parts by mass of the rubber
And 12 parts of rubber flame retardant trans-1, 2-dibromoethylene, the mixture is isolated from air and water at the temperature of 35 ℃, the reaction is carried out for 4 hours, and glue solution after the reaction is removed by a solvent to obtain a flame-retardant plasticizer product with Mn of 1700;
adding 100g of the prepared flame-retardant plasticizer product, 0.5g of emulsifier potassium fatty acid and 400g of desalted water into an emulsifier, controlling the temperature to be 15 ℃, and stirring to prepare a plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: 7.8 are mixed to prepare mixed latex, and 1.5 parts by mass of coagulant Al is added at the reaction temperature of 12 DEG C2(SO4)3Coagulating, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
The Mooney viscosity is reduced from 55 to 38 and the oxygen index is increased from 19.7% to 29.3% through tests.
Comparative example 5:
compared with the embodiment 5, the other conditions are the same, except that the fire retardant is added in the liquid phase mixing procedure, specifically: nitrile rubber NBR3305 was dissolved in chloroform to prepare a 3.75% solution, and 0.85 part by mass of an olefin metathesis catalyst was added to 100 parts by mass of the rubber
Isolating air and water at 35 ℃, reacting for 4 hours, and removing the reacted glue solution through a solvent to obtain a flame-retardant plasticizer product with Mn of 10300;
adding 100g of the prepared flame-retardant plasticizer product, 12 parts of rubber flame retardant trans-1, 2-dibromoethene equivalent to the plasticizer, 0.5g of emulsifier potassium fatty acid and 400g of desalted water into an emulsifier, controlling the temperature to be 15 ℃, and stirring to prepare a plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: 7.8 are mixed to prepare mixed latex, and 1.5 parts by mass of coagulant Al is added at the reaction temperature of 12 DEG C2(SO4)3Coagulating, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
Tests show that the Mooney viscosity is reduced from 55 to 49, the oxygen index is increased from 19.7% to 20.9%, and the dibromoethene is decomposed in white smoke during coagulation and drying.
Example 6:
nitrile butadiene rubber NBR3305 was dissolved in chlorobenzene solvent to prepare a 19% w solution, and 0.95 part by mass of olefin metathesis catalyst was added to 100 parts by mass of rubber
And 38 parts of rubber flame retardant chloroethylene, and reacting for 3.23 hours at the temperature of 28 ℃ under the condition of air and water isolation, wherein after the reactionRemoving the glue solution by using a solvent to obtain a flame-retardant plasticizer product with Mn of 900;
adding 100g of the prepared flame-retardant plasticizer product, 0.2g of emulsifier potassium fatty acid and 443g of desalted water into an emulsifier, controlling the temperature to be 78 ℃, and stirring to prepare a plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: 1.3 mixing to prepare mixed latex, and adding 5.5 parts by mass of coagulant Al at the reaction temperature of 35 DEG C2(SO4)3Coagulating, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
The Mooney viscosity is reduced from 55 to 49.5 and the oxygen index is increased from 19.7% to 24.7%.
Comparative example 6:
compared with the example 6, the other conditions are the same, except that di-2-ethylhexyl phthalate is adopted as a plasticizer, and a flame retardant is added, specifically: 100g of di-2-ethylhexyl phthalate plasticizer, 0.2g of emulsifier fatty acid potassium, 443g of desalted water and 38 parts of rubber flame retardant vinyl chloride relative to the mass of the plasticizer are added into an emulsifier, the temperature is controlled to be 78 ℃, and the mixture is stirred to prepare plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulating kettle according to a dry basis ratio of 100: 1.3, mixing to prepare mixed latex, adding 5.5 parts by mass of coagulant at the reaction temperature of 35 ℃ for coagulation, washing, centrifugally dewatering and drying to prepare the easily processed flame-retardant nitrile rubber.
The Mooney viscosity is reduced from 55 to 53, the oxygen index is not obviously changed, and white smoke generated by decomposing vinyl chloride is generated during agglomeration and drying.
Example 7:
nitrile butadiene rubber NBR3305 was dissolved in chlorobenzene solvent to prepare 18% w solution, and 0.95 parts by mass of olefin metathesis catalyst was added to 100 parts by mass of rubber
And 43 parts of a rubber flame retardant vinyl bromide, air excluded at 48 ℃ andreacting for 3.5 hours by using water, and removing the glue solution after the reaction by using a solvent to obtain a flame-retardant plasticizer product with the Mn of 550;
adding 100g of the prepared flame-retardant plasticizer product, 0.29g of emulsifier potassium fatty acid and 98g of desalted water into an emulsifier, controlling the temperature to be 63 ℃, and stirring to prepare a plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: 33 are mixed to prepare a mixed latex, 21 parts by mass of a coagulant Ca (HSO) is added at a reaction temperature of 55 DEG C4)2Coagulating, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
The Mooney viscosity is reduced from 55 to 39 and the oxygen index is increased from 19.7% to 28.7% through tests.
Comparative example 7:
compared with the example 7, the other conditions are the same, except that the double decomposition catalyst is added in the preparation process of the plasticizer for reaction, then the flame retardant is added for reaction for a period of time, and the specific steps are as follows: nitrile butadiene rubber NBR3305 was dissolved in chlorobenzene solvent to prepare 18% w solution, and 0.95 parts by mass of olefin metathesis catalyst was added to 100 parts by mass of rubber
Isolating air and water at 48 ℃ for reacting for 2h, adding 43 parts of rubber flame retardant vinyl bromide, isolating air and water at 48 ℃, reacting for 1.5 h, and removing the reacted glue solution through a solvent to obtain a flame-retardant plasticizer product with Mn of 9500;
adding 100g of the prepared flame-retardant plasticizer product, 0.29g of emulsifier potassium fatty acid and 98g of desalted water into an emulsifier, controlling the temperature to be 63 ℃, and stirring to prepare a plasticizer emulsion;
adding latex and plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: 33 are mixed to prepare a mixed latex, 21 parts by mass of a coagulant Ca (HSO) is added at a reaction temperature of 55 DEG C4)2Coagulating, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
The Mooney viscosity is reduced from 55 to 50 and the oxygen index is increased from 19.7% to 21.3% through tests.
Claims (16)
1. A preparation method of easy-to-process flame-retardant nitrile rubber comprises the following specific steps:
1) preparing a flame-retardant plasticizer, dissolving nitrile rubber in a solvent to prepare 0.1-20 w% of solution, adding 0.5-1.5 parts of olefin metathesis catalyst and 10-60 parts of rubber flame retardant based on 100 parts by mass of rubber, isolating air and water at 15-50 ℃, reacting for 0.5-5 hours, and removing the reacted glue solution through the solvent to obtain a flame-retardant plasticizer product; the rubber flame retardant is an organic halide monomer containing an ethylenically unsaturated substituent;
2) mixing the prepared flame-retardant plasticizer product with an emulsifier and water, and stirring to prepare a plasticizer emulsion;
3) adding latex and flame-retardant plasticizer emulsion into a coagulation kettle, stirring, and mixing according to a dry basis ratio of 100: 1-50, mixing to prepare mixed latex, adding 1-25 parts by mass of coagulant at the reaction temperature of 10-80 ℃ for coagulation, washing, centrifugally dewatering and drying to obtain the easily processed flame-retardant nitrile rubber.
2. The process for preparing nitrile rubber according to claim 1, wherein the flame retardant plasticizer has an Mn of 200-8000.
3. The process for preparing nitrile rubber according to claim 1, wherein the solvent is a solvent capable of dissolving nitrile rubber which does not contain an olefin in its structure.
4. The process for the preparation of nitrile rubbers according to claim 1, wherein the solvent is selected from chloroform, chlorobenzene, acetone or butanone.
5. The process for producing a nitrile rubber according to claim 1, wherein in the production of the flame-retardant plasticizer, 0.8 to 1.2 parts by mass of an olefin metathesis catalyst is added to 100 parts by mass of the nitrile rubber.
6. The process for preparing nitrile rubber according to claim 1, wherein 15 to 35 parts by mass of a rubber flame retardant is added to 100 parts by mass of nitrile rubber in the preparation of the flame-retardant plasticizer.
7. The process for preparing nitrile rubber according to claim 1, wherein the rubber flame retardant has the formula: RX; wherein: r contains an unsaturated olefin aliphatic chain segment with 2-18 carbon atoms; x is F, Cl, Br or I.
8. The method for preparing nitrile rubber according to claim 7, wherein R in the formula of the rubber flame retardant is selected from the group consisting of vinyl, propenyl, isopropenyl, isopentenyl, 3-pentenyl, 6-octenyl, trimethylvinyl, 1-heptenyl, methacryloxypropyl, and methacryloxy.
9. The process for preparing nitrile rubber according to claim 7, wherein R in the formula of the rubber flame retardant is vinyl.
10. The process for preparing nitrile rubber according to claim 7, wherein X in the formula of the rubber flame retardant is Br.
11. The process for preparing nitrile rubber according to claim 7, wherein R in the formula of the rubber flame retardant contains a cyano group.
12. The process for preparing nitrile rubber according to claim 1, wherein the rubber flame retardant is selected from vinyl chloride, chlorinated acrylonitrile, brominated acrylonitrile or vinyl bromide.
13. The process for preparing a nitrile rubber according to claim 1, wherein the olefin metathesis catalyst is a metal carbene catalyst having an olefin metathesis function.
14. The process for the preparation of nitrile rubbers according to claim 1, wherein the olefin metathesis catalyst is selected from the group consisting of (o-isopropoxybenzylidene) (tricyclohexylphosphine) ruthenium (II) dichloride
Dichloro [ o-isopropoxybenzylidene ] group][1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolinylidene]Ruthenium complex
15. The process for the preparation of nitrile rubbers according to claim 1, characterized in that the emulsifiers are saturated or unsaturated fatty acid soaps or rosin acid soaps; the dosage of the flame retardant plasticizer is 0.1-20 parts by weight added to 100 parts of flame retardant plasticizer product.
16. The process for the preparation of nitrile rubber according to claim 1, wherein said coagulant is selected from the group consisting of CaCl2、MgSO4、Mg Cl2、Al2(SO4)3、FeCl3、CuCl2、Ca(HSO4)2The dosage of the one or the mixture is 1 to 25 parts by mass of 100 parts of butyronitrile latex.
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| CN102603928A (en) * | 2011-01-11 | 2012-07-25 | 赞南科技(上海)有限公司 | Preparation method of hydrogenated nitrile rubber and degradation and hydrogenation method of butadiene type rubber |
| US20120252982A1 (en) * | 2011-03-30 | 2012-10-04 | Zannan Scitech Co., Ltd. | Methods of modifying polymers with highly active and selective metathesis catalysts |
| CN103339181A (en) * | 2011-02-03 | 2013-10-02 | 日本瑞翁株式会社 | Nitrile rubber composition, crosslinking nitrile rubber composition, and crosslinked rubber product |
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| CN102603928A (en) * | 2011-01-11 | 2012-07-25 | 赞南科技(上海)有限公司 | Preparation method of hydrogenated nitrile rubber and degradation and hydrogenation method of butadiene type rubber |
| CN103339181A (en) * | 2011-02-03 | 2013-10-02 | 日本瑞翁株式会社 | Nitrile rubber composition, crosslinking nitrile rubber composition, and crosslinked rubber product |
| US20120252982A1 (en) * | 2011-03-30 | 2012-10-04 | Zannan Scitech Co., Ltd. | Methods of modifying polymers with highly active and selective metathesis catalysts |
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