CN105837754A - Preparation method of carboxyl nitrile rubber - Google Patents
Preparation method of carboxyl nitrile rubber Download PDFInfo
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- CN105837754A CN105837754A CN201510020981.0A CN201510020981A CN105837754A CN 105837754 A CN105837754 A CN 105837754A CN 201510020981 A CN201510020981 A CN 201510020981A CN 105837754 A CN105837754 A CN 105837754A
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- Prior art keywords
- nitrile rubber
- preparation
- carboxy terminated
- terminated nitrile
- add
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Links
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 59
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 48
- 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 27
- 238000006243 chemical reaction Methods 0.000 claims description 44
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 21
- 229920000126 latex Polymers 0.000 claims description 18
- 239000004816 latex Substances 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 14
- 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
- -1 aryl sulphur Chemical compound 0.000 claims description 9
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical group [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical group [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- 238000001816 cooling Methods 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 compound [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
- 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 5
- 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 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052767 actinium Inorganic materials 0.000 claims description 4
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical group OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- 229950010248 loretin Drugs 0.000 claims description 3
- 239000012875 nonionic emulsifier Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 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
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 235000010352 sodium erythorbate Nutrition 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 150000008051 alkyl sulfates Chemical group 0.000 claims 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 238000006073 displacement reaction Methods 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 229940051841 polyoxyethylene ether Drugs 0.000 claims 1
- 229920000056 polyoxyethylene ether Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 229920001971 elastomer Polymers 0.000 abstract description 6
- 239000005060 rubber Substances 0.000 abstract description 6
- 238000003878 thermal aging Methods 0.000 abstract 1
- 239000004636 vulcanized rubber Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000011056 performance test Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 150000002825 nitriles Chemical class 0.000 description 5
- 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 4
- 239000002253 acid Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000002156 mixing Methods 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
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 description 2
- CKDAPHXLBCKEKI-UHFFFAOYSA-N C=CC=C.C(=O)(O)C(C#N)=C Chemical compound C=CC=C.C(=O)(O)C(C#N)=C CKDAPHXLBCKEKI-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 210000000481 breast Anatomy 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- NFPBWZOKGZKYRE-UHFFFAOYSA-N 2-propan-2-ylperoxypropane Chemical compound CC(C)OOC(C)C NFPBWZOKGZKYRE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- UFOFRAGRYOYPKN-UHFFFAOYSA-N hydrogen peroxide;propylbenzene Chemical compound OO.CCCC1=CC=CC=C1 UFOFRAGRYOYPKN-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 230000000704 physical effect Effects 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect 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
- 238000010092 rubber production Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 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
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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 high nitrile carboxy lower content in the preparation method of a kind of carboxy terminated nitrile rubber, particularly one
The preparation method of carboxy terminated nitrile rubber, belongs to field of polymer technology.
Background technology
Carboxy terminated nitrile rubber (XNBR) is because introducing carboxyl in nitrile rubber, so its oil resistivity enters one
Step strengthens, and the introducing of carboxyl simultaneously also improves the hot strength of nitrile rubber, tearing strength, elastic modelling quantity
And hardness, wearability, cohesiveness and ozone-resistant aging, particularly improve drawing under nitrile rubber high temperature
Stretch intensity.It addition, introduce carboxyl can also improve the polarity of nitrile rubber molecule, increase and polrvinyl chloride, phenol
The compatibility of urea formaldehyde etc..XNBR is mainly used in prepare and oil resistivity and wearability is required higher rubber
In goods, binding agent, machine components, such as aircraft, automobile and important plant equipment dynamic sealing, height
Laminate seal, wearing piece, oil resistant part, it is possible to be blended resistance to improve it with PVC, CR, NBR etc.
Oiliness and wearability.
About the synthesis of carboxy terminated nitrile rubber, just deliver by fourth two as far back as Brown and Duke in 1954
Alkene, acrylonitrile, methacrylic acid ternary polymerization prepare the research of carboxy terminated nitrile rubber, the U.S. in 1956
B.F.Goodrich chemical industrial company first batch produces carboxy terminated nitrile rubber, at present, and the main fourth in the world
The most German bright Sheng of nitrile rubber manufacturer, south, Taiwan Supreme Being, Japanese auspicious father-in-law etc. can produce carboxy terminated nitrile rubber, main
All to be prepared from by ternary emulsion copolymerization by butadiene, acrylonitrile, unsaturated carboxylic acid or carboxylic esters,
And concrete formula and the vital strategic secrets of technique Dou Shige producer.
US2003109642 describes under couplant or condensing agent effect, comprises at least one unsaturated altogether
The polymer of yoke diene, unsaturated nitrile and unsaturated carboxylic acid monomer, can simultaneously selective hydrogenation and crosslinking
Method, hydrogenation only selects at carbochain double-bond hydrogenation, can avoid the hydrogenation of the itrile group in polymer or carboxyl, this
Plant special polymeric material and there is the performance of excellence.JP2000026547 describes a kind of soap-free emulsion and gathers
Close preparation carboxy terminated nitrile rubber method, this patent primary object be (1) 1,3-butadiene, acrylonitrile,
The reaction of methacrylic acid binary polymerization occurs at the reactor adding potassium peroxydisulfate water-soluble polymer medium
In, total inventory at least accounts for the 60% of reactor volume；(2) in order to be prepared into seeding polymerization latex, instead
Should carry out at 25～80 DEG C, until solid content reaches 20%；(3) in seed latex, 1,3-fourth is added
Diene, acrylonitrile, potassium peroxydisulfate, be polymerized 1 hour thus be prepared into second polymer medium；(4)
Second polymer medium continues to react and is finally prepared into carboxylic acrylonitrile butadiene rubber latex at least half an hour.
EP0955324A1 also describes a kind of method that emulsifier-free emulsion polymerization prepares carboxylic acrylonitrile butadiene rubber latex, and
JP2000026547 belongs to patent families.
Domestic all have been reported that in terms of carboxy terminated nitrile rubber production technology and processed and applied.Moral as great in Shandong Zibo
Chemical Co., Ltd. uses the quaternary carboxy terminated nitrile rubber technology of Qingdao University of Science and Technology's independent research to build up 4000
Ton/year carboxy terminated nitrile rubber process units；(" the middle nitrile group content low-molecular-weight carboxy terminated nitrile rubber such as neat Yongxin
Synthesis ", New Chemical Materials, 2012, (9): 21-23 page) use butadiene, acrylonitrile, third
Olefin(e) acid carries out binary polymerization, and potassium peroxydisulfate is initiator, and mercaptan is regulator, uses middle temperature (30 DEG C～40
DEG C) emulsion synthesized low-molecular-weight (Mn=1000～2000) carboxy terminated nitrile rubber；Li Xiao waits by force (" carboxylic
The performance study of base nitrile rubber ", rubber industry, 2004, (2): 69-73 page) have studied carboxyl fourth
The vulcanization characteristics of nitrile rubber and physical property；Patent CN200510042123.2 discloses a kind of carboxyl butyronitrile
The preparation method of latex, uses butadiene, acrylonitrile, unsaturated carboxylic acid and unsaturated carboxylic acid fat, 40～
50 DEG C, cause persulfate, carry out polymerization and prepare carboxylated latex；Patent CN200710199290.7 is public
Open a kind of carboxylic acrylonitrile butadiene rubber latex preparation method and application, used sectional temperature-controlled, add desalted water, breast in batches
Agent and the mode of regulator, initial temperature is 25 ± 2 DEG C, is warming up to 40 ± 1 DEG C after having added for the first time,
Second time is warming up to 55 ± 1 DEG C after adding, and conversion ratio terminates when reaching more than 99%, is prepared into carboxyl butyronitrile glue
Breast；Patent CN200510029573.8 discloses the preparation method of a kind of carboxylic acrylonitrile butadiene rubber latex, uses fourth two
Alkene, acrylonitrile, unsaturated carboxylic acid and unsaturated carboxylic acid fat, polymerization temperature 5～9 DEG C, different by hydrogen peroxide
Propyl benzene causes, and emulsifying agent uses the mode in batches added, and conversion ratio terminates when reaching 90%, is prepared into carboxyl fourth
Nitrile latex；Patent CN97107122.5 discloses the preparation technology of a kind of carboxyl acrylonitrile-butadiene rubber powder, first by
Butadiene, acrylonitrile, at 45～75 DEG C, are prepared nitrile rubber latex by sulfate initiation, then 65～70
Under the conditions of DEG C, add containing carboxyl and peroxide thereof, be prepared into micropowder shape suspension, treated obtain carboxyl
Acrylonitrile-butadiene rubber powder.
Summary of the invention
It is an object of the invention to provide a kind of method preparing carboxy terminated nitrile rubber.The carboxyl that the present invention obtains
Nitrile rubber has hardness height, wearability and heat-resistant aging is good, gel content is low and physical synthesis performance is excellent
Strength and extension property under different feature, particularly high temperature is outstanding than the performance of common nitrile rubber, and product can be used
In key areas such as national defence chemical industry.
The preparation method of carboxy terminated nitrile rubber of the present invention comprises the steps:
In polymeric kettle, in terms of total monomer weight 100 parts, add water, emulsifying agent, activator, 27～33
Part acrylonitrile, 0.5～5 part of unsaturated carboxylic acid, 0.2～2.0 part of molecular weight regulator, evacuation, nitrogen are put
After changing, add oxygen scavenger and 62～72.5 parts of butadiene, be subsequently adding 0.02～0.25 part of initiator and carry out
Polyreaction, respectively adds acrylonitrile, initiator and molecule when polymerisation conversion reaches 40%～75%
Amount regulator, additional amount is acrylonitrile 5～7 parts, initiator 0.005～0.015 part, molecular weight regulator
0.06～0.12 part, when conversion ratio reaches 80%～84%, add terminator cooling discharge, prepare
Carboxylic acrylonitrile butadiene rubber latex, through condensing, washing, is dried, prepares carboxy terminated nitrile rubber product.
The preferred conversion ratio of acrylonitrile of the present invention reaches to add when 40%～50%, and initiator preferably converts
Rate reaches to add when 65%～70%, and the preferred conversion ratio of molecular weight regulator reaches to add when 70%～75%.
Unsaturated carboxylic acid of the present invention, mainly methacrylic acid or acrylic acid, its addition is ability
Territory conventional amount used, the present invention is not specially limited, as long as it can occur poly-with acrylonitrile and butadiene monomer
Conjunction reacting generating copolymer.Its consumption preferably metering system in terms of total monomer weight 100 parts in the present invention
Acid is 0.5～2.0 part, and acrylic acid is 2.0～5.0 parts.
Emulsifying agent of the present invention is emulsifying agent stable in acid medium, and alternative have alkyl sulfide
Hydrochlorate and alkyl or aryl sulfonate, this anion emulsifier, as primary emulsion, also needs same nonionic
Property emulsifying agent compound, compounding than being 1:3.0～8.0, non-ionic emulsifier is alternative polyoxy
Vinyl Ether, anhydrous sorbitol tristearate, β-how sodium sulfonate and the condensation substance of formaldehyde, collectively constitute multiple
Closing emulsification system, need to add a kind of strong acid, the preferred concentrated sulphuric acid of the present invention simultaneously, PH is 5.0～6.5 in regulation.
Its addition is this area conventional amount used, and the present invention is not specially limited, and the present invention is preferably with total monomer weight
100 parts are calculated as 2.0～5.0 parts, more preferably 2.8～3.5 parts.
Initiator of the present invention is redox initiator, alternative have cumyl hydroperoxide,
Di-isopropylbenzene hydroperoxide, the isopropyl peroxide tert-butyl ester, isopropyl peroxide N-butyl, preferably peroxidating
Hydrogen diisopropylbenzene (DIPB).Initiator amount is this area conventional amount used, and the present invention is preferably with total monomer weight 100 parts
It is calculated as 0.02～0.25 part, more preferably 0.05～0.15 part.
Activator of the present invention, mainly has Diao Bai block, ferrous sulfate, EDTA tetrasodium salt or EDTA
Ferrum sodium salt etc., consumption is this area conventional amount used, the present invention preferably with total monomer weight 100 parts be calculated as 0.05～
0.3 part, more preferably 0.1～0.2 part.
Molecular weight regulator of the present invention is the regulator that emulsion polymerization is general, preferably uncle 12 carbon sulfur
Alcohol, consumption is this area conventional amount used, and the present invention is preferably calculated as 0.2～2.0 part with total monomer weight 100 parts,
More preferably 0.6～1.0 part.
Oxygen scavenger of the present invention mainly has sodium dithionite, DMKO, arabo-ascorbic acid, carbon
Hydrazides, N-isopropylhydroxyla etc., preferably oxygen scavenger is sodium dithionite, and consumption is this area conventional amount used,
The present invention is preferably calculated as 0.005～0.02 part with total monomer weight 100 parts.
Terminator of the present invention is not particularly limited, and alternative terminator has sodium nitrite, actinium ferrum
Reagent or P-aminoazobenzene etc., consumption is this area conventional amount used, and the present invention is preferably with total monomer weight
100 parts are calculated as 0.05～0.5 part.
Total monomer weight of the present invention is the weight of acrylonitrile, butadiene and unsaturated carboxylic acid.
The scope that polymeric reaction temperature of the present invention can be used selected from Conventional cryogenic emulsion polymerization,
The present invention preferably 4～6 DEG C.
" part " of being not specifically noted in the present invention each means weight portion.
Use the carboxy terminated nitrile rubber that is prepared into of the inventive method, its rubber bound acrylonitrile content be 32.0～
35.0%, Mooney viscosity is 45～55, and carboxyl-content is 0.2～1.2%, gel content ＜ 1.0%, sulfuration
Glue has wearability, heat aging and the physical and mechanical properties of excellence, and the particularly strength and extension property under high temperature is outstanding
For remarkably.
Detailed description of the invention
Following example and the same formula of the mixing employing of comparative example rubber and technique, mixing formula see table 1.
Table 1 rubber mixing formula
Following example and each performance measurement of comparative example perform standard and are shown in Table 2
Table 2 project bioassay standard
| 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 |
| Hot 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 |
Further describe the present invention by embodiment below, but the present invention is not limited in embodiment.
Embodiment 1
15L band stir pressure still adds 240 parts of desalted waters, 3.2 parts of dodecylbenzene sodium sulfonate soaps,
0.12 part of Diao Bai block, 0.03 part of EDTA-ferrum sodium salt, 0.05 part of EDTA-4Na salt, 31 parts of monomer propylene
Nitrile, 2 parts of methacrylic acids and 0.56 part of tert-dodecyl mercaptan, after evacuation, replace three times with nitrogen, then
Adding 0.01 part of oxygen scavenger sodium dithionite, 67 parts of monomer butadiene, still temperature to be polymerized drops to 5 DEG C
Time, add 0.075 part of initiator di-isopropylbenzene hydroperoxide, start polyreaction, during control polymerization
Reaction temperature, at 4 DEG C, surveyed a dry every 2 hours, and polymerisation conversion reaches to add 6.0 when 43%
Part acrylonitrile, continues reaction, and polymerisation conversion reaches to add 0.005 part of initiator when 66%, and conversion ratio reaches
Adding 0.08 part of regulator during to 72%, conversion ratio reaches to add terminator sodium nitrite when 82.9%, stirs
Mixing cooling discharge half an hour, latex is through cohesion, dried, and the performance test results is listed in table 3.
Embodiment 2
15L band stir pressure still adds 220 parts of desalted waters, 3.0 parts of sodium lauryl sulphate soaps, 0.10
Part Diao Bai block, 0.02 portion of EDTA-ferrum sodium salt, 0.06 portion of EDTA-4Na salt, 30 parts of monomers acrylonitrile,
5 parts of acrylic acid and 0.60 part of tert-dodecyl mercaptan, after evacuation, replace three times with nitrogen, add 0.01
Part oxygen scavenger sodium dithionite, 65 parts of monomer butadiene, when still temperature to be polymerized drops to 5 DEG C, add
0.07 part of initiator di-isopropylbenzene hydroperoxide, start polyreaction, during control polymeric reaction temperature exist
5 DEG C, surveying a dry every 2 hours, polymerisation conversion reaches to add 5.0 parts of acrylonitrile when 47%,
Continuing reaction, polymerisation conversion reaches to add 0.01 part of initiator when 68%, and conversion ratio reaches to mend when 73%
Adding 0.07 part of regulator, conversion ratio reaches to add when 83.2% terminator actinium ferron, stirring cooling half an hour
Discharging, latex is through cohesion, dried, and the performance test results is listed in table 3.
Embodiment 3
15L band stir pressure still adds 200 parts of desalted waters, 3.1 parts of dodecylbenzene sodium sulfonate soaps,
0.14 part of Diao Bai block, 0.03 part of EDTA-ferrum sodium salt, 0.04 part of EDTA-4Na salt, 28.5 parts of monomers third
Alkene nitrile, 2 parts of acrylic acid and 0.58 part of tert-dodecyl mercaptan, after evacuation, replace three times with nitrogen, then add
Enter 0.01 part of oxygen scavenger sodium dithionite, 69.5 parts of monomer butadiene, when still temperature to be polymerized drops to 6 DEG C,
Add 0.06 part of initiator cumyl hydroperoxide, start polyreaction, during control polyreaction temperature
Degree, at 5 ± 1 DEG C, surveyed a dry every 2 hours, and polymerisation conversion reaches to add when 45% 7.0 parts
Acrylonitrile, continues reaction, and polymerisation conversion reaches to add 0.01 part of initiator hydrogen peroxide isopropyl when 67%
Benzene, conversion ratio reaches to add 0.10 part of regulator when 74%, and conversion ratio reaches to add terminator when 81.7%
Actinium ferron, stirring cooling discharge half an hour, latex is through cohesion, dried, and the performance test results is listed in table
3。
Embodiment 4
15L band stir pressure still adds 260 parts of desalted waters, 3.3 parts of dodecylbenzene sodium sulfonate soaps,
0.14 part of Diao Bai block, 0.05 part of EDTA-ferrum sodium salt, 0.02 part of EDTA-4Na salt, 33 parts of monomer propylene
Nitrile, 0.8 part of methacrylic acid and 0.62 part of tert-dodecyl mercaptan, after evacuation, replace three times with nitrogen,
Adding 0.01 part of oxygen scavenger sodium dithionite, 66.2 parts of monomer butadiene, still temperature to be polymerized drops to 5
DEG C time, add 0.08 part of initiator di-isopropylbenzene hydroperoxide, start polyreaction, during control poly-
Conjunction reaction temperature, at 5 DEG C, surveyed a dry every 2 hours, and polymerisation conversion reaches to add when 46%
5.0 parts of acrylonitrile, continue reaction, and polymerisation conversion reaches to add 0.005 part of initiator peroxidating when 68%
Hydrogen diisopropylbenzene (DIPB), conversion ratio reaches to add 0.08 part of regulator when 71%, and conversion ratio reaches to add when 83.5%
Entering terminator sodium nitrite, stirring cooling discharge half an hour, latex is through cohesion, dried, and performance test is tied
Fruit is listed in table 3.
Table 3 embodiment cured properties test result
Comparative example 1
The common nitrile rubber of NBR3305 selecting Lanzhou Petrochemical Company to produce carries out performance comparison,
NBR3305 the performance test results is shown in Table 4, NBR3305 air aging and hot test results of property and is shown in Table
5。
Table 4 comparative example 1 the performance test results
Table 5 comparative example 1 air aging and hot test results of property
Comparative example 1 result shows: chooses Mooney viscosity and combines common close with product of the present invention of nitrile content
Nitrile rubber NBR3305 contrasts, carboxy terminated nitrile rubber prepared by the present invention either in mechanical property,
Or the strength and extension property under its wearability, resistance to air aging properties and high temperature, is all significantly better than common
NBR3305, thus widened the range of application of carboxy terminated nitrile rubber further.
Comparative example 2
Polymerization temperature controls at 6.5 DEG C, and other formula and technique are same as in Example 1, is prepared into carboxyl fourth
Nitrile rubber properties of product the results are shown in Table 6.
Table 6 comparative example 2 the performance test results
Comparative example 2 result shows: when polymerization temperature is more than 6 DEG C, and response speed is substantially accelerated, and strand is sent out
Raw branched crosslinking increases, and gel rises rapidly, and Mooney viscosity raises, and product mechanics degradation, latex is steady
Qualitative decline, is unfavorable for storage and the conveying of latex.
Comparative example 3
Other polymerization formulas and technique are same as in Example 1, and monomers acrylonitrile uses the mode once added,
Properties of product the results are shown in Table 7.
Table 7 comparative example 3 the performance test results
Comparative example 3 result of the test shows: monomers acrylonitrile once adds fashionable, makes carboxyl at polymer molecular chain
Combination rate reduces, and also can affect the carboxyl distribution at strand simultaneously, indirectly cause product comprehensive mechanical property
Decline.
Comparative example 4
Other polymerization formulas and technique are same as in Example 2, and initiator uses and once adds, and prepares carboxylic
Base nitrile rubber properties of product the results are shown in Table 8.
Table 8 comparative example 4 the performance test results
Comparative example 4 result shows: initiator uses and once adds, and polyreaction early stage is very fast, late phase reaction
Slow especially, the conversion ratio of regulation to be reached, polymerization reaction time need to be greatly prolonged, cause being polymerized the later stage and coagulate
Glue significantly rises, and production efficiency is low, and the final binding capacity of acrylonitrile of identical proportioning is the most relatively dividedly in some parts initiator
Time low.
Comparative example 5
Other polymerization formulas and technique are the same as in Example 4, and molecular weight regulator uses the side once added
Formula, properties of product are shown in Table 9.
Table 9 comparative example 5 the performance test results
Comparative example 5 result shows: molecular weight regulator employing once adds fashionable, to product Mooney viscosity influence
Not quite, but product microstructure and molecular weight distribution there are is considerable influence, once add regulating effect ratio in batches
Adding regulating effect poor, the reaction later stage causes polymer molecular chain to increase, and branched crosslinking increases, gel content
Rise, make product combination property decline.
Comparative example 6,7
Other polymerization formulas and technique are the same as in Example 4, when conversion ratio reaches 50% or 80% respectively, mend
Adding molecular weight regulator, properties of product are shown in Table 10.
Table 10 comparative example 6,7 the performance test results
Comparative example 6,7 result shows: molecular weight regulator adds opportunity, to product Mooney viscosity and microcosmic
Structure has certain impact, adds molecular weight regulator, can cause rubber before or after conversion ratio of the present invention
Mooney viscosity, combine nitrile content and carboxyl-content fluctuation, gel content rise, product combination property decline.
Comparative example 8,9,10
The final conversion ratio of polyreaction is respectively 84.5%, 85.3%, 86.4%, other polymerization formulas and technique
Same as in Example 3, under the conditions of differentiated yields, properties of product the results are shown in Table 11.
Table 11 comparative example 8,9,10 properties of product are tested
Comparative example 8,9,10 result shows: when conversion ratio is more than 84%, product Mooney viscosity, gel
Content all steeply rises, and conversion ratio the most up increases by 1%, and it is the fastest that gel rises, and hot strength increase is not
Greatly, but Mooney viscosity dramatically increases, and elongation at break is greatly reduced, and makes product plasticate and poor processability.
Claims (12)
1. the preparation method of a carboxy terminated nitrile rubber, it is characterised in that comprise the steps: at polymeric kettle
In, in terms of total monomer 100 weight portion, add water, emulsifying agent, activator, 27～33 parts of acrylonitrile,
0.5～5 part of unsaturated carboxylic acid, 0.2～2.0 part of molecular weight regulator, after the displacement of evacuation, nitrogen, add
Oxygen scavenger and 62～72.5 parts of butadiene, be subsequently adding 0.02～0.25 part of initiator and carry out polyreaction,
Acrylonitrile, initiator and molecular weight regulator is respectively added when polymerisation conversion reaches 40%～75%,
When conversion ratio reaches 80%～84%, add terminator cooling discharge, prepare carboxylic acrylonitrile butadiene rubber latex,
Through condensing, washing, it is dried, prepares carboxy terminated nitrile rubber product.
The preparation method of carboxy terminated nitrile rubber the most according to claim 1, it is characterised in that: described
Acrylonitrile add when conversion ratio reaches 40%～50%, additional amount is 5～7 parts.
The preparation method of carboxy terminated nitrile rubber the most according to claim 1, it is characterised in that: described
Initiator add when conversion ratio reaches 65%～70%, additional amount is 0.005～0.015 part.
The preparation method of carboxy terminated nitrile rubber the most according to claim 1, it is characterised in that: described
Molecular weight regulator add when conversion ratio reaches 70%～75%, additional amount is 0.06～0.12 part.
The preparation method of carboxy terminated nitrile rubber the most according to claim 1, it is characterised in that: described
Unsaturated carboxylic acid is methacrylic acid or acrylic acid, and methacrylic acid consumption is 0.5～2.0 part, and acrylic acid is used
Amount is 2.0～5.0 parts.
The preparation method of carboxy terminated nitrile rubber the most according to claim 1, it is characterised in that: described
Emulsifying agent is the composite emulsifier of anion emulsifier and non-ionic emulsifier, anion emulsifier and non-from
The proportioning of sub-property emulsifying agent is 1:3.0～8.0, and anion emulsifier is alkyl sulfate and alkyl or aryl sulphur
Hydrochlorate, non-ionic emulsifier is polyoxyethylene ether, anhydrous sorbitol tristearate, the sodium sulfonate of β-how
With the condensation substance of formaldehyde, emulsifier is 2.0～5.0 parts.
The preparation method of carboxy terminated nitrile rubber the most according to claim 1, it is characterised in that: described
Initiator is cumyl hydroperoxide, di-isopropylbenzene hydroperoxide, the isopropyl peroxide tert-butyl ester or peroxidating
Isopropyl N-butyl, its consumption is 0.02～0.25 part
The preparation method of carboxy terminated nitrile rubber the most according to claim 1, it is characterised in that: described
Activator is one or more in Diao Bai block, ferrous sulfate, EDTA tetrasodium salt or NaFeEDTA sodium salt,
Its consumption is 0.05～0.3 part.
The preparation method of carboxy terminated nitrile rubber the most according to claim 1, it is characterised in that: described
Molecular weight regulator is tert-dodecyl mercaptan, and its consumption is 0.2～2.0 part.
The preparation method of carboxy terminated nitrile rubber the most according to claim 1, it is characterised in that: described
Oxygen scavenger is sodium dithionite, DMKO, arabo-ascorbic acid, carbohydrazide or N-isopropylhydroxyla,
Its consumption is 0.005～0.02 part.
The preparation method of 11. carboxy terminated nitrile rubber according to claim 1, it is characterised in that: described
Terminator is sodium nitrite, actinium ferron or P-aminoazobenzene, and its consumption is 0.05～0.5 part.
The preparation method of 12. carboxy terminated nitrile rubber according to claim 1, it is characterised in that: described
Polymeric reaction temperature is 4～6 DEG C.
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