CN105837754B - Preparation method of carboxyl nitrile rubber - Google Patents
Preparation method of carboxyl nitrile rubber Download PDFInfo
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- CN105837754B CN105837754B CN201510020981.0A CN201510020981A CN105837754B CN 105837754 B CN105837754 B CN 105837754B CN 201510020981 A CN201510020981 A CN 201510020981A CN 105837754 B CN105837754 B CN 105837754B
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- nitrile rubber
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- carboxy nitrile
- emulsifier
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- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 56
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims description 46
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- 239000003995 emulsifying agent Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 150000001735 carboxylic acids Chemical class 0.000 claims description 11
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical class [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012875 nonionic emulsifier Substances 0.000 claims description 5
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- 150000001450 anions Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical group CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 3
- 210000000481 breast Anatomy 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- NFPBWZOKGZKYRE-UHFFFAOYSA-N 2-propan-2-ylperoxypropane Chemical compound CC(C)OOC(C)C NFPBWZOKGZKYRE-UHFFFAOYSA-N 0.000 claims description 2
- QPQKUYVSJWQSDY-CCEZHUSRSA-N 4-(phenylazo)aniline Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=CC=C1 QPQKUYVSJWQSDY-CCEZHUSRSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005228 aryl sulfonate group Chemical group 0.000 claims description 2
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000007859 condensation product Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 235000010352 sodium erythorbate Nutrition 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 125000005526 alkyl sulfate group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims 1
- 235000010265 sodium sulphite Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 229920001971 elastomer Polymers 0.000 abstract description 10
- 239000005060 rubber Substances 0.000 abstract description 10
- 238000003878 thermal aging Methods 0.000 abstract 1
- 239000004636 vulcanized rubber Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- 229920000126 latex Polymers 0.000 description 16
- 239000004816 latex Substances 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000011056 performance test Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 230000003750 conditioning effect Effects 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 5
- 150000008360 acrylonitriles Chemical class 0.000 description 4
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 229910052767 actinium Inorganic materials 0.000 description 3
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- ZBJWWKFMHOAPNS-UHFFFAOYSA-N loretin Chemical compound C1=CN=C2C(O)=C(I)C=C(S(O)(=O)=O)C2=C1 ZBJWWKFMHOAPNS-UHFFFAOYSA-N 0.000 description 3
- 229950010248 loretin Drugs 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 235000019394 potassium persulphate Nutrition 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010092 rubber production Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- HJCCZIABCSDUPE-UHFFFAOYSA-N methyl 2-[4-[[4-methyl-6-(1-methylbenzimidazol-2-yl)-2-propylbenzimidazol-1-yl]methyl]phenyl]benzoate Chemical compound CCCC1=NC2=C(C)C=C(C=3N(C4=CC=CC=C4N=3)C)C=C2N1CC(C=C1)=CC=C1C1=CC=CC=C1C(=O)OC HJCCZIABCSDUPE-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Abstract
The invention relates to a preparation method of carboxyl nitrile rubber, the carboxyl nitrile rubber prepared by the method has the raw rubber combined acrylonitrile content of 32.0-35.0%, the Mooney viscosity of 45-55, the carboxyl content of 0.2-1.2% and the gel content of less than 1.0%, and vulcanized rubber has excellent wear resistance, thermal aging resistance and physical and mechanical properties, particularly excellent high-temperature tensile and elongation properties.
Description
Technical field
The present invention relates to a kind of preparation methods of carboxy nitrile rubber, especially high nitrile carboxy lower content carboxyl fourth in one kind
The preparation method of nitrile rubber, belongs to the field of polymers.
Background technology
Carboxy nitrile rubber (XNBR) in nitrile rubber because introducing carboxyl, so its oil resistivity further enhances, together
When carboxyl introducing also improve tensile strength, tearing strength, elasticity modulus and hardness, wearability, the adherence of nitrile rubber
With ozone-resistant aging, the tensile strength under nitrile rubber high temperature is especially improved.In addition, butyronitrile can also be improved by introducing carboxyl
The polarity of rubber molecule increases the compatibility with polyvinyl chloride, phenolic resin etc..XNBR be mainly used in preparation to oil resistivity and
In the more demanding rubber product of wearability, adhesive, machine components, as aircraft, automobile and important mechanical equipment dynamic are close
Sealing, high-pressure sealing ring, wearing piece, oil resistant part can be also blended with PVC, CR, NBR etc. to improve its oil resistivity and wear-resisting
Property.
Synthesis in relation to carboxy nitrile rubber, early in Brown and Duke in 1954 just delivered by butadiene, acrylonitrile,
Methacrylic acid ternary polymerization prepares the research of carboxy nitrile rubber, and B.F.Goodrich chemical industrial companies of the U.S. are first within 1956
First batch produces carboxy nitrile rubber, currently, the main nitrile rubber manufacturer in the world such as bright Sheng of Germany, Taiwan south Supreme Being, Japan
Auspicious father-in-law etc. can produce carboxy nitrile rubber, all be mainly to pass through ternary by butadiene, acrylonitrile, unsaturated carboxylic acid or carboxylic esters
Emulsion copolymerization is prepared, and be specifically formulated and technique be all each producer vital strategic secrets.
US2003109642 is described under couplant or condensing agent effect, including at least one unsaturated and conjugated diolefin,
The polymer of unsaturated nitrile and unsaturated carboxylic acid monomer, simultaneous selection add hydrogen and crosslinked method, hydrogen are added only to select
Carbochain double-bond hydrogenation, can avoid the hydrogenation of the itrile group or carboxyl in polymer, and this special polymer material has excellent
Performance.JP2000026547 describes a kind of method that emulsifier-free emulsion polymerization prepares carboxy nitrile rubber, the patent main inventive
Point is that (1) 1,3- butadiene, acrylonitrile, the reaction of methacrylic acid binary polymerization are happened at and add potassium peroxydisulfate water-soluble poly
In the reaction kettle of hydrate medium, total inventory at least accounts for the 60% of reactor volume；(2) in order to be prepared into seeding polymerization latex,
Reaction need to carry out at 25~80 DEG C, until solid content is up to 20%；(3) added in seed latex 1,3- butadiene, acrylonitrile,
Potassium peroxydisulfate polymerize 1 hour to be prepared into second polymer medium；(4) the reaction was continued in second polymer medium
At least half an hour is finally prepared into carboxylic acrylonitrile butadiene rubber latex.EP0955324A1 also describes a kind of emulsifier-free emulsion polymerization and prepares carboxyl
The method and JP2000026547 of NBR latex belong to patent families.
The country all has been reported that in terms of carboxy nitrile rubber production technology and processed and applied.As the great Dehua work of Shandong Zibo has
Limit company builds up 4000 tons/year of carboxy nitrile rubber using the quaternary carboxy nitrile rubber technology of Qingdao University of Science and Technology's independent research
Process units；Neat Yongxin etc. (" synthesis of middle nitrile group content low molecular weight carboxy nitrile rubber ", New Chemical Materials, 2012,
(9)：21-23 pages) using butadiene, acrylonitrile, acrylic acid progress binary polymerization, potassium peroxydisulfate is initiator, and mercaptan is to adjust
Agent has synthesized low molecular weight (Mn=1000~2000) carboxy nitrile rubber using medium temperature (30 DEG C~40 DEG C) emulsion polymerization；Lee
Dawn strong grade (" performance study of carboxy nitrile rubber ", rubber industry, 2004, (2)：69-73 pages) have studied carboxy nitrile rubber
Vulcanization characteristics and physical property；Patent CN200510042123.2 discloses a kind of preparation method of carboxylic acrylonitrile butadiene rubber latex, adopts
Caused by persulfate at 40~50 DEG C with butadiene, acrylonitrile, unsaturated carboxylic acid and unsaturated carboxylic acid fat, carries out polymerization system
Standby carboxylated latex；Patent CN200710199290.7 discloses a kind of carboxylic acrylonitrile butadiene rubber latex preparation method and application, using segmentation
Temperature control adds the mode of desalted water, emulsifier and conditioning agent in batches, and initial temperature is 25 ± 2 DEG C, heating after having added for the first time
To 40 ± 1 DEG C, it is warming up to 55 ± 1 DEG C after adding for the second time, is terminated when conversion ratio is up to 99% or more, is prepared into carboxyl butyronitrile glue
Breast；Patent CN200510029573.8 discloses a kind of preparation method of carboxylic acrylonitrile butadiene rubber latex, using butadiene, acrylonitrile, no
Saturated carboxylic acid and unsaturated carboxylic acid fat, 5~9 DEG C of polymerization temperature, are caused by cumyl hydroperoxide, and emulsifier is used and added in batches
Mode, terminated when conversion ratio is up to 90%, be prepared into carboxylic acrylonitrile butadiene rubber latex；Patent CN97107122.5 discloses a kind of carboxyl fourth
The preparation process of nitrile rubber powder prepares nitrile rubber glue at 45~75 DEG C by butadiene, acrylonitrile by sulfuric acid salt inducement first
Breast, then under the conditions of 65~70 DEG C, be added and contain carboxyl and its peroxide, be prepared into micro mist shape suspension, obtain carboxylic through processing
Base acrylonitrile-butadiene rubber powder.
Invention content
The purpose of the present invention is to provide a kind of methods preparing carboxy nitrile rubber.The carboxyl butyronitrile rubber that the present invention obtains
Glue has the characteristics that hardness is high, wearability and heat-resistant aging are good, gel content is low and physical synthesis is had excellent performance, especially high
Strength and extension property under temperature is more outstanding than the performance of common nitrile rubber, and product can be used for the key areas such as national defence chemical industry.
The preparation method of carboxy nitrile rubber of the present invention includes the following steps：
In polymeric kettle, in terms of 100 parts of total monomer weight, be added water, emulsifier, activator, 27~33 parts of acrylonitrile,
0.5~5 part of unsaturated carboxylic acid, 0.2~2.0 part of molecular weight regulator vacuumize, after nitrogen displacement, be added oxygen scavenger and 62~
Then 72.5 parts of butadiene are added 0.02~0.25 part of initiator and carry out polymerisation, when polymerisation conversion reaches 40%~
An acrylonitrile, initiator and molecular weight regulator are respectively added when 75%, additional amount is 5~7 parts of acrylonitrile, initiator 0.005
~0.015 part, 0.06~0.12 part of molecular weight regulator are added terminator and cool down when conversion ratio reaches 80%~84%
Material, is prepared carboxylic acrylonitrile butadiene rubber latex, through cohesion, washing, drying, carboxy nitrile rubber product is prepared.
The preferred conversion ratio of acrylonitrile of the present invention is added when reaching 40%~50%, and the preferred conversion ratio of initiator reaches
It is added when 65%~70%, molecular weight regulator preferred conversion ratio is added when reaching 70%~75%.
Unsaturated carboxylic acid of the present invention, mainly methacrylic acid or acrylic acid, addition are this field routines
Dosage, the present invention are not specially limited, as long as polymerisation, which can occurs, with acrylonitrile and butadiene monomer in it generates polymer
.Its dosage is preferably by methacrylic acid in terms of 100 parts of total monomer weight for 0.5~2.0 part in the present invention, acrylic acid 2.0
~5.0 parts.
Emulsifier of the present invention be in acid medium stablize emulsifier, it is alternative have alkyl sulfate and
Alkyl or aryl sulfonate, the anion emulsifier also need same non-ionic emulsifier to be compounded as primary emulsion,
Compounding is than being 1:3.0~8.0, non-ionic emulsifier is alternative have polyoxyethylene ether, anhydrous sorbitol tristearate,
β-how the condensation product of sodium sulfonate and formaldehyde, collectively constitute composite emulsifying system, while a kind of strong acid need to be added, the present invention is preferred
The concentrated sulfuric acid adjusts PH 5.0~6.5.Its addition is this field conventional amount used, and the present invention is not specially limited, and the present invention is excellent
100 parts with total monomer weight of choosing is calculated as 2.0~5.0 parts, more preferable 2.8~3.5 parts.
Initiator of the present invention is redox initiator, alternative to have cumyl hydroperoxide, peroxidating
Hydrogen diisopropylbenzene (DIPB), the isopropyl peroxide tert-butyl ester, isopropyl peroxide N-butyl, preferably di-isopropylbenzene hydroperoxide.Initiator
Dosage is this field conventional amount used, and the present invention is preferably calculated as 0.02~0.25 part with 100 parts of total monomer weight, more preferable 0.05~
0.15 part.
Activator of the present invention mainly has Diao Bai blocks, ferrous sulfate, EDTA tetrasodium salts or NaFeEDTA sodium salt etc., uses
Amount is this field conventional amount used, and the present invention is preferably calculated as 0.05~0.3 part with 100 parts of total monomer weight, more preferable 0.1~0.2
Part.
Molecular weight regulator of the present invention is the general conditioning agent of emulsion polymerization, preferably tert-dodecyl mercaptan, dosage
For this field conventional amount used, the present invention preferably with total monomer weight 100 parts be calculated as 0.2~2.0 part, more preferable 0.6~1.0 part.
Oxygen scavenger of the present invention mainly has sodium dithionite, dimethyl ketone oxime, arabo-ascorbic acid, carbohydrazide, N-
Isopropylhydroxyla etc., preferably oxygen scavenger are sodium dithionite, and dosage is this field conventional amount used, and the present invention is preferably total with monomer
100 parts of weight is calculated as 0.005~0.02 part.
Terminator of the present invention is not particularly limited, alternative terminator have sodium nitrite, actinium ferron or
P-aminoazobenzene etc., dosage be this field conventional amount used, the present invention preferably with total monomer weight 100 parts be calculated as 0.05~0.5
Part.
Total monomer weight of the present invention is the weight of acrylonitrile, butadiene and unsaturated carboxylic acid.
Polymeric reaction temperature of the present invention can be selected from range used by Conventional cryogenic emulsion polymerization, the present invention
It is preferred that 4~6 DEG C.
" part " being not specifically noted in the present invention each means parts by weight.
The carboxy nitrile rubber being prepared into using the method for the present invention, raw rubber bound acrylonitrile content be 32.0~
35.0%, Mooney viscosity is 45~55, and carboxyl-content is 0.2~1.2%, and gel content ＜ 1.0%, vulcanizate has excellent
Strength and extension property under wearability, heat aging and physical mechanical property, especially high temperature is particularly splendid.
Specific implementation mode
Following embodiment and comparative example raw rubber, which are kneaded, uses same formula and technique, mixing formula to see the table below 1.
1 raw rubber mixing formula of table
Following embodiment and each performance measurement of comparative example execute standard and are shown in Table 2
2 project bioassay standard of table
| Analysis project | Execution standard |
| Mooney viscosity ML (1+4,100 DEG C) | GB/T 1232.1-2000 |
| In conjunction with nitrile content, ω % | SH/T 1157-1997 |
| Tensile strength, MPa | GB/T 528-2009 |
| 300% stress at definite elongation, MPa | GB/T 528-2009 |
| Elongation at break, % | GB/T 528-2009 |
| Wearability, cm3/km | GB/T 1689-1998 |
| Hot air aging | GB/T 3512-2001 |
| Gel content, ω % | SH/T 1050-91 |
| Shao's A hardness | GB/T 531.1-2008 |
Using embodiment below, present invention be described in more detail, but the present invention is not limited in embodiment.
Embodiment 1
240 parts of desalted waters, 3.2 parts of neopelex soaps, 0.12 part of Diao Bai is added in the pressure-resistant kettle of 15L band stirrings
Block, 0.03 portion of EDTA- ferrisodiums salt, 0.05 portion of EDTA-4Na salt, 31 parts of monomers acrylonitriles, 2 parts of methacrylic acids and 0.56 part of uncle
DDM dodecyl mercaptan after vacuumizing, three times with nitrogen displacement, adds 0.01 part of oxygen scavenger sodium dithionite, 67 parts of monomer fourths
Diene when kettle temperature degree to be polymerized drops to 5 DEG C, is added 0.075 part of initiator di-isopropylbenzene hydroperoxide, starts polymerisation, mistake
Polymeric reaction temperature is controlled in journey at 4 DEG C, surveys a dry matter every 2 hours, polymerisation conversion adds 6.0 when reaching 43%
Part acrylonitrile, the reaction was continued, and polymerisation conversion adds 0.005 part of initiator when reaching 66%, and conversion ratio is added when reaching 72%
Terminator sodium nitrite is added when reaching 82.9% in 0.08 part of conditioning agent, conversion ratio, stirs half an hour cooling discharge, latex is through solidifying
After poly-, dry, the performance test results are listed in table 3.
Embodiment 2
220 parts of desalted waters, 3.0 parts of lauryl sodium sulfate soaps, 0.10 part of Diao Bai is added in the pressure-resistant kettle of 15L band stirrings
Block, 0.02 portion of EDTA- ferrisodiums salt, 0.06 portion of EDTA-4Na salt, 30 parts of monomers acrylonitriles, 5 parts of acrylic acid and 0.60 part of uncle 12
Carbon mercaptan after vacuumizing, three times with nitrogen displacement, adds 0.01 part of oxygen scavenger sodium dithionite, 65 parts of monomer butadiene,
When kettle temperature degree to be polymerized drops to 5 DEG C, 0.07 part of initiator di-isopropylbenzene hydroperoxide is added, starts polymerisation, controls in the process
Polymeric reaction temperature processed surveys a dry matter at 5 DEG C, every 2 hours, and polymerisation conversion adds 5.0 parts of propylene when reaching 47%
Nitrile, the reaction was continued, and polymerisation conversion adds 0.01 part of initiator when reaching 68%, and conversion ratio adds 0.07 part of tune when reaching 73%
Agent is saved, conversion ratio is added terminator actinium ferron when reaching 83.2%, stirs half an hour cooling discharge, latex is through agglomerating, drying
Afterwards, the performance test results are listed in table 3.
Embodiment 3
200 parts of desalted waters, 3.1 parts of neopelex soaps, 0.14 part of Diao Bai is added in the pressure-resistant kettle of 15L band stirrings
Block, 0.03 portion of EDTA- ferrisodiums salt, 0.04 portion of EDTA-4Na salt, 28.5 parts of monomers acrylonitriles, 2 parts of acrylic acid and 0.58 part of uncle ten
Two carbon mercaptan after vacuumizing, three times with nitrogen displacement, add 0.01 part of oxygen scavenger sodium dithionite, 69.5 parts of monomer fourths
Diene when kettle temperature degree to be polymerized drops to 6 DEG C, is added 0.06 part of initiator cumyl hydroperoxide, starts polymerisation, in the process
Polymeric reaction temperature is controlled at 5 ± 1 DEG C, surveys a dry matter every 2 hours, polymerisation conversion adds 7.0 when reaching 45%
Part acrylonitrile, the reaction was continued, and polymerisation conversion adds 0.01 part of initiator cumyl hydroperoxide when reaching 67%, and conversion ratio reaches
0.10 part of conditioning agent is added when to 74%, terminator actinium ferron, stirring half an hour cooling is added in conversion ratio when reaching 81.7%
Discharging, for latex after agglomerating, drying, the performance test results are listed in table 3.
Embodiment 4
260 parts of desalted waters, 3.3 parts of neopelex soaps, 0.14 part of Diao Bai is added in the pressure-resistant kettle of 15L band stirrings
Block, 0.05 portion of EDTA- ferrisodiums salt, 0.02 portion of EDTA-4Na salt, 33 parts of monomers acrylonitriles, 0.8 part of methacrylic acid and 0.62 part
Tert-dodecyl mercaptan after vacuumizing, three times with nitrogen displacement, adds 0.01 part of oxygen scavenger sodium dithionite, 66.2 parts of lists
Body butadiene when kettle temperature degree to be polymerized drops to 5 DEG C, is added 0.08 part of initiator di-isopropylbenzene hydroperoxide, starts polymerisation,
Control polymeric reaction temperature surveys a dry matter, polymerisation conversion is added when reaching 46% at 5 DEG C every 2 hours in the process
5.0 parts of acrylonitrile, the reaction was continued, and polymerisation conversion adds 0.005 part of initiator di-isopropylbenzene hydroperoxide when reaching 68%, turns
Rate adds 0.08 part of conditioning agent when reaching 71%, terminator sodium nitrite is added in conversion ratio when reaching 83.5%, stirring half is small
When cooling discharge, for latex after agglomerating, drying, the performance test results are listed in table 3.
3 embodiment cured properties test result of table
Comparative example 1
The common nitrile rubbers of NBR3305 of Lanzhou Petrochemical Company production are selected to carry out performance comparison, NBR3305 performance tests
It the results are shown in Table 4, NBR3305 air agings and hot test results of property be shown in Table 5.
4 comparative example of table, 1 the performance test results
5 comparative example of table, 1 air aging and hot test results of property
Comparative example 1 the result shows that：It chooses Mooney viscosity and combines nitrile content and common butyronitrile rubber similar in product of the present invention
Glue NBR3305 is compared, and carboxy nitrile rubber prepared by the present invention is either in mechanical property or its wearability, resistance to sky
Strength and extension property under gas aging and high temperature is all significantly better than common NBR3305, to further widen carboxy nitrile rubber
Application range.
Comparative example 2
Polymerization temperature is controlled at 6.5 DEG C, other formulas and technique are same as Example 1, is prepared into carboxy nitrile rubber production
Moral character can the results are shown in Table 6.
6 comparative example of table, 2 the performance test results
Comparative example 2 the result shows that：When polymerization temperature is more than 6 DEG C, reaction speed is obviously accelerated, and branched crosslinking occurs for strand
Increase, gel rises rapidly, and Mooney viscosity increases, and product mechanical property is deteriorated, and latex stability declines, and is unfavorable for the storage of latex
It deposits and conveys.
Comparative example 3
Other polymerization formulas and technique are same as Example 1, and monomers acrylonitrile is by the way of being once added, properties of product
It the results are shown in Table 7.
7 comparative example of table, 3 the performance test results
3 test result of comparative example shows：When monomers acrylonitrile is once added, carboxyl is made to be dropped in polymer molecular chain Percentage bound
It is low, while distribution of the carboxyl in strand can be also influenced, cause product comprehensive mechanical property to decline indirectly.
Comparative example 4
Other polymerization formulas and technique are same as Example 2, and initiator is added using primary, and carboxyl butyronitrile rubber is prepared
Glue properties of product the results are shown in Table 8.
8 comparative example of table, 4 the performance test results
Comparative example 4 the result shows that：Initiator is added using primary, and polymerisation is very fast early period, and late phase reaction is especially slow,
Reach defined conversion ratio, polymerization reaction time need to be greatly prolonged, causes polymerization later stage gel to significantly rise, production efficiency
Low, the final binding capacity of acrylonitrile of identical proportioning is also low compared with when being added portionwise initiator.
Comparative example 5
Other polymerization formulas and technique are same as Example 4, and molecular weight regulator is by the way of being once added, product
9 can be shown in Table.
9 comparative example of table, 5 the performance test results
Comparative example 5 the result shows that：It is little to product Mooney viscosity influence when molecular weight regulator is using primary be added, but
There is larger impact to product microstructure and molecular weight distribution, it is primary regulating effect ratio to be added to be added portionwise regulating effect poor, instead
Answer the later stage that polymer molecular chain is caused to increase, branched crosslinking increases, and gel content rises, and product comprehensive performance is made to decline.
Comparative example 6,7
Other polymerization formulas and technique are same as Example 4, conversion ratio respectively up to 50% or 80% when, add molecular weight tune
Agent is saved, properties of product are shown in Table 10.
10 comparative example 6 of table, 7 the performance test results
Comparative example 6,7 the result shows that：Molecular weight regulator adds opportunity, has centainly to product Mooney viscosity and microstructure
Influence, molecular weight regulator added before or after conversion ratio of the present invention, crude rubber Mooney viscosity can be caused, in conjunction with nitrile content and
Carboxyl-content fluctuates, and gel content rises, and product comprehensive performance declines.
Comparative example 8,9,10
The final conversion ratio of polymerisation is respectively 84.5%, 85.3%, 86.4%, other polymerization formulas and technique and implementation
Example 3 is identical, and under the conditions of differentiated yields, properties of product the results are shown in Table 11.
11 comparative example of table, 8,9,10 properties of product are tested
Comparative example 8,9,10 the result shows that：When conversion ratio is more than 84%, product Mooney viscosity, gel content all drastically on
It rises, conversion ratio is per up increasing by 1%, and gel rises faster, and tensile strength increases less, but Mooney viscosity dramatically increases, and pulls
Disconnected elongation is greatly reduced, and product is made to plasticate and poor processability.
Claims (12)
1. a kind of preparation method of carboxy nitrile rubber, it is characterised in that include the following steps：In polymeric kettle, with total monomer
100 parts by weight meters, be added water, emulsifier, activator, 27~33 parts of acrylonitrile, 0.5~5 part of unsaturated carboxylic acid, 0.2~2.0 part
Molecular weight regulator vacuumizes, after nitrogen displacement, oxygen scavenger and 62~72.5 parts of butadiene is added, then it is added 0.02~
0.25 part of initiator carries out polymerisation, and acrylonitrile, an initiator are respectively added when polymerisation conversion reaches 40%~75%
And molecular weight regulator is added terminator cooling discharge, carboxyl butyronitrile glue is prepared when conversion ratio reaches 80%~84%
Carboxy nitrile rubber product is prepared through cohesion, washing, drying in breast.
2. the preparation method of carboxy nitrile rubber according to claim 1, it is characterised in that：The acrylonitrile is converting
Rate is added when reaching 40%~50%, and additional amount is 5~7 parts.
3. the preparation method of carboxy nitrile rubber according to claim 1, it is characterised in that：The initiator is converting
Rate is added when reaching 65%~70%, and additional amount is 0.005~0.015 part.
4. the preparation method of carboxy nitrile rubber according to claim 1, it is characterised in that：The molecular weight regulator
It is added when conversion ratio reaches 70%~75%, additional amount is 0.06~0.12 part.
5. the preparation method of carboxy nitrile rubber according to claim 1, it is characterised in that：The unsaturated carboxylic acid is first
Base acrylic acid or acrylic acid, methacrylic acid dosage are 0.5~2.0 part, and acrylic acid dosage is 2.0~5.0 parts.
6. the preparation method of carboxy nitrile rubber according to claim 1, it is characterised in that：The emulsifier is anion
The quality proportioning of the composite emulsifier of emulsifier and non-ionic emulsifier, anion emulsifier and non-ionic emulsifier is 1:
3.0~8.0, anion emulsifier is alkyl sulfate and alkyl or aryl sulfonate, and non-ionic emulsifier is polyoxyethylene
The condensation product of ether, anhydrous sorbitol tristearate, β-sodium naphthalene sulfonate and formaldehyde, emulsifier are 2.0~5.0 parts.
7. the preparation method of carboxy nitrile rubber according to claim 1, it is characterised in that：The initiator is peroxidating
Hydrogen isopropylbenzene, di-isopropylbenzene hydroperoxide, the isopropyl peroxide tert-butyl ester or isopropyl peroxide N-butyl, dosage 0.02
~0.25 part.
8. the preparation method of carboxy nitrile rubber according to claim 1, it is characterised in that：The activator is Diao Bai
One or more of block, ferrous sulfate, EDTA tetrasodium salts or NaFeEDTA sodium salt, dosage are 0.05~0.3 part.
9. the preparation method of carboxy nitrile rubber according to claim 1, it is characterised in that：The molecular weight regulator is
Tert-dodecyl mercaptan, dosage are 0.2~2.0 part.
10. the preparation method of carboxy nitrile rubber according to claim 1, it is characterised in that：The oxygen scavenger is to connect two
Sodium sulfite, dimethyl ketone oxime, arabo-ascorbic acid, carbohydrazide or N- isopropylhydroxylas, dosage are 0.005~0.02 part.
11. the preparation method of carboxy nitrile rubber according to claim 1, it is characterised in that：The terminator is nitrous
Sour sodium or P-aminoazobenzene, dosage are 0.05~0.5 part.
12. the preparation method of carboxy nitrile rubber according to claim 1, it is characterised in that：The polymeric reaction temperature
It is 4~6 DEG C.
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| CN115043980B (en) * | 2021-03-08 | 2023-06-30 | 中国石油天然气股份有限公司 | Method for preparing cold-resistant thermoplastic elastomer by emulsion polymerization method and prepared silicon-containing thermoplastic elastomer |
| CN115043997B (en) * | 2021-03-08 | 2023-07-25 | 中国石油天然气股份有限公司 | Method for preparing carboxyl-containing thermoplastic elastomer by emulsion polymerization method and prepared thermoplastic elastomer |
| CN113563515B (en) * | 2021-06-30 | 2024-04-09 | 江西岳峰集团环保新材有限公司 | Preparation method of high-performance carboxylated nitrile latex |
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