CN118165144A - Hydrogenated latex and preparation method and application thereof - Google Patents
Hydrogenated latex and preparation method and application thereof Download PDFInfo
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- 229920000126 latex Polymers 0.000 title claims abstract description 82
- 239000004816 latex Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 43
- 229920001971 elastomer Polymers 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000005060 rubber Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000000839 emulsion Substances 0.000 claims abstract description 3
- 238000005086 pumping Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 14
- 150000001993 dienes Chemical class 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- -1 propyl hydroxypropyl Chemical group 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- 229940117986 sulfobetaine Drugs 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 2
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 2
- DQTNMAJBVQZYDZ-UHFFFAOYSA-N CCCCCCCCCCCC(C)(C)[NH2+]C(CC)S([O-])(=O)=O Chemical compound CCCCCCCCCCCC(C)(C)[NH2+]C(CC)S([O-])(=O)=O DQTNMAJBVQZYDZ-UHFFFAOYSA-N 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000005110 aryl thio group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229960003237 betaine Drugs 0.000 claims description 2
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- GABKKRHRVUPBFK-UHFFFAOYSA-N ethoxy(methoxy)methanesulfonic acid Chemical compound CCOC(OC)S(=O)(=O)O GABKKRHRVUPBFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- URXQDXAVUYKSCK-UHFFFAOYSA-N hexadecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[NH+](C)C URXQDXAVUYKSCK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- QEALYLRSRQDCRA-UHFFFAOYSA-N myristamide Chemical compound CCCCCCCCCCCCCC(N)=O QEALYLRSRQDCRA-UHFFFAOYSA-N 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002174 Styrene-butadiene Substances 0.000 description 8
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 8
- 229920003051 synthetic elastomer Polymers 0.000 description 6
- 239000005061 synthetic rubber Substances 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- 239000011115 styrene butadiene Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 240000000233 Melia azedarach Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides hydrogenated latex, a preparation method and application thereof. The preparation method comprises the following steps: pumping the solution A and the latex into a micro-reactor respectively for continuous reaction to prepare hydrogenated latex; wherein solution a comprises a hydrogenation catalyst, an emulsifier and a solvent; the latex is emulsion containing unsaturated rubber; the mass ratio of the hydrogenation catalyst to the unsaturated rubber is not less than 0.4%; the mass ratio of the emulsifier to the unsaturated rubber is not less than 0.2%; the temperature of the continuous reaction is not lower than 50 ℃, and the pressure is not lower than 2MPa; the equivalent diameter of the channel in the microreactor is not higher than 4mm; the flow rate ratio of latex to solution a pumped into the microreactor is not higher than 30:1. The obtained hydrogenated latex has high hydrogenation degree and high stability and excellent mechanical properties; the whole preparation method is simple and feasible, has low cost and low energy consumption, and has high production efficiency.
Description
Technical Field
The invention relates to the technical field of rubber elastomers, in particular to hydrogenated latex, and a preparation method and application thereof.
Background
The various diene polymers are elastomers with excellent performance, and Styrene Butadiene Rubber (SBR), nitrile Butadiene Rubber (NBR), butadiene rubber, polyisoprene, styrene butadiene block copolymer (SBS) and the like are all important synthetic rubbers. However, these synthetic rubbers have unsaturated carbon-carbon double bonds in the molecule, and therefore, they are relatively poor in heat resistance and weather resistance. In this way, the unsaturated carbon-carbon double bond can be hydrogenated and modified, the thermal-oxidative aging resistance of the synthetic rubber is obviously improved after the double bond is saturated, and the mechanical property of the synthetic rubber is correspondingly changed due to the change of the chain structure.
The hydrogenation of diene polymer synthetic rubber is carried out by adopting a solution method in industry, and the preparation conditions are that in a pressure vessel, noble metal complex such as Rh or Pd is used as a catalyst, and the synthetic rubber is subjected to solution hydrogenation at high temperature or high pressure, so that the method has the defects of long flow, high cost and high energy consumption on the whole.
Therefore, it is highly desirable to develop a simple, low cost, low energy consumption continuous hydrogenation process for conjugated diene based latex.
Disclosure of Invention
In order to solve the defects in the prior art of conjugated diene latex hydrogenation, the invention provides hydrogenated latex and a preparation method and application thereof. The hydrogenated latex obtained by the preparation method has high hydrogenation degree and high stability and also has excellent mechanical properties; the whole preparation method is simple and feasible, low in cost and energy consumption, and has high production efficiency.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of hydrogenated latex, which comprises the following steps: pumping solution A and latex into a micro-reactor respectively for continuous reaction to obtain hydrogenated latex; wherein,
The solution A comprises a hydrogenation catalyst, an emulsifier and a solvent;
the latex is emulsion containing unsaturated rubber;
The mass ratio of the hydrogenation catalyst to the unsaturated rubber is not less than 0.4%;
The mass ratio of the emulsifier to the unsaturated rubber is not less than 0.2%;
the temperature of the continuous reaction is not lower than 50 ℃, and the pressure is not lower than 2MPa;
The equivalent diameter of the channel in the microreactor is not higher than 4mm;
The flow rate ratio of the latex to the solution A pumped into the microreactor is not higher than 30:1.
In the invention, the mass ratio means the ratio of the total mass of all raw materials in the whole continuous feeding process, namely, the feeding is started to the end of continuous reaction.
In the present invention, the structural formula of the hydrogenated latex may include a fragment as shown in formula 1 and/or formula 2:
wherein a, b, c, d, e, f, g, h and i are both degrees of polymerization, each independently is an integer greater than or equal to 1.
In the present invention, the degree of hydrogenation of the hydrogenated latex may be not less than 90%, preferably not less than 95%, for example 96%, 97% or 98%.
In the present invention, the tensile strength of the hydrogenated latex may be not lower than 20MPa, preferably 20 to 30MPa, for example, 20.2MPa, 21.8MPa, 23.4MPa, 23.5MPa, 23.6MPa, 24.5MPa or 24.8MPa.
In the present invention, the hydrogenated latex may have an elongation at break of not more than 400%, preferably 350% to 400%, for example 366.0%, 367.4%, 368.4%, 370.1%, 370.8%, 371.7% or 387.5%.
In the present invention, the 300% elongation stress of the hydrogenated latex may be not less than 3MPa, preferably 3 to 4MPa, for example 3.5MPa, 3.6MPa or 3.7MPa.
Wherein the tensile strength, elongation at break and 300% elongation stress of the hydrogenated latex are all determined with reference to GB/T528 2009.
In the present invention, the mass ratio of the hydrogenation catalyst to the unsaturated rubber may be 0.4% to 8%, preferably 2% to 8%, more preferably 2% to 5%.
In the present invention, the mass ratio of the surfactant to the unsaturated rubber may be 0.2% to 5.5%, preferably 0.5% to 5.5%, more preferably 1% to 2%.
In the present invention, the temperature of the continuous reaction may be 50℃to 150℃and preferably 80℃to 100 ℃.
In the present invention, the pressure of the continuous reaction may be 2 to 10MPa, preferably 3 to 6MPa.
In the invention, the microreactor has the characteristics of small channel size and channel diversity, and fluid flows in the channels, and has very large surface area/volume ratio when reacting, thereby realizing the effects of high reaction efficiency, accurate control, continuous production and the like.
In the present invention, the equivalent diameter of the channels in the microreactor is preferably less than 3mm.
In the present invention, the flow rate at which the latex is pumped into the microreactor is 10 to 500mL/min, preferably 50 to 300mL/min.
In the present invention, the flow rate of the solution A pumped into the microreactor is 10-100mL/min, preferably 10-50mL/min.
In the present invention, the ratio of the flow rates of the latex and the solution A pumped into the microreactor is (1-30): 1, preferably (10-20): 1.
In the present invention, the volume of the microreactor may be selected according to the flow rate at which each raw material is pumped into the microreactor, and the specific meaning thereof will be known to those skilled in the art.
In the present invention, the solids content of the unsaturated rubber in the latex may be less than 55%, preferably 40% to 50%, the percentages being by mass. The remainder of the latex is a volatilizable solvent, such as water, the specific meaning of which will be known to those skilled in the art.
In the present invention, the unsaturated rubber may mean a rubber containing an unsaturated carbon-carbon double bond, and is preferably a conjugated diene polymer-based rubber.
Wherein the conjugated diene polymer rubber is preferably selected from one or more of natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), acrylonitrile-butadiene copolymer (NBR), butadiene-isoprene, butadiene-acrylonitrile-butyl acrylate terpolymer, and butadiene-acrylonitrile-acrylic acid terpolymer, more preferably styrene-butadiene copolymer (SBR) and/or acrylonitrile-butadiene copolymer (NBR).
In the present invention, the emulsifier may be selected from one or more of amphoteric betaines, cationic surfactants, anionic surfactants, and nonionic surfactants.
Wherein the amphoteric betaine is preferably selected from one or more of 3-N, N (dimethyldodecylamino) -propane sulfonate, tetradecylamide propyl hydroxypropyl sulfobetaine and decane-dimethyl hydroxypropyl sulfobetaine.
Wherein the cationic surfactant is preferably selected from cetyl dimethyl ammonium chloride and/or stearyl trimethyl ammonium chloride.
Wherein the anionic surfactant is preferably selected from one or more of sodium dodecyl sulfate, sodium fatty alcohol polyoxyethylene ether sulfate and sodium laurylsulfate.
Wherein the nonionic surfactant is preferably selected from fatty alcohol polyoxyethylene ether and/or alkylphenol polyoxyethylene ether.
In the present invention, the structural formula of the hydrogenation catalyst may be represented by formula 3 or formula 4:
wherein M may be a group VIII metal element, preferably ruthenium (Ru) or osmium (Os), such as ruthenium.
Wherein, the X 1、X2 may each be independently selected from an anionic ligand, preferably one of Cl, CF 3COO、CH3 COO, tosylate (p-CH 3-C6H4-SO3)、(CF3)(CH3)2 CO, phenoxy, CFH 2COO、(CH3)3 CO, methoxy, ethoxy, mesylate (CH 3SO3) and triflate (CF 3SO3), for example Cl.
Wherein, L can be an uncharged electron donor, and the structural formula of L is shown in formula 5:
Wherein, R 1 can be selected from one of hydrogen, alkyl, alkenyl, alkynyl and aryl.
Wherein, the R 2、R3、R4 and R 5 may each be independently selected from one of hydrogen, halogen, nitro, CF 3、C1-C30 alkyl, C 3-C20 alkynyloxy, C 2-C20 alkenyl, C 2-C20 alkynyl, C 6-C24 aryl, C 1-C20 alkoxy, C 2-C20 alkenyloxy, C 2-C20 alkynyloxy, C 6-C24 aryloxy, C 2-C20 alkoxycarbonyl, C 1-C20 alkylamino, C 1-C20 alkylthio, C 6-C24 arylthio, C 1-C20 alkylsulfonyl and C 1-C20 alkylsulfinyl.
Wherein, Y can be selected from one of O, S, N and P groups.
Wherein, R 6、R7 and R 8 can each be independently selected from one or more of alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl and alkylsulfinyl.
In some embodiments, the dehydrogenation catalyst has a structural formula as shown in formula 6:
In some embodiments, the dehydrogenation catalyst has a structural formula as shown in formula 7:
In the present invention, the continuous reaction may be carried out under an inert atmosphere, for example, under a nitrogen atmosphere.
In the present invention, the solvent may be water and methylene chloride, and the weight ratio of the water to the methylene chloride is preferably 9:1.
In the present invention, after the completion of the continuous reaction, it is preferable to further include a step of removing the solvent, which is preferably performed under reduced pressure.
The present invention also provides a hydrogenated latex obtained by the preparation method as described above.
The invention also provides an application of the hydrogenated latex in the automobile manufacturing field, the wire and cable field or the medical appliance field.
In the present invention, the application in the field of automobile manufacture may include the production of automobile tires from the hydrogenated latex.
In the present invention, the application in the field of electric wires and cables may include using the hydrogenated latex as a coating material for electric wires and cables.
In the present invention, the application in the field of medical devices may include the production of surgical devices, infusion sets, syringes, medical bandages and the like from the hydrogenated latex.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
The preparation method of the invention is a continuous hydrogenation production method of carbon-carbon double bonds in latex, and the prepared hydrogenated latex has high hydrogenation degree and high stability and also has excellent mechanical properties (tensile strength, elongation at break and 300% stretching stress); the method can improve the product stability among batches, and simultaneously improve the production efficiency and the process safety, and the whole preparation method is simple and easy to implement, has relatively mild reaction conditions, low cost and low energy consumption, and can realize that the hydrogenation degree of the hydrogenated latex reaches more than 90 percent without generating gel.
Drawings
FIG. 1 is a comparison of the IR spectra of the latex of example 1 before and after hydrogenation.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The reagents or equipment used were not manufacturer-noted and were conventional products available for purchase by regular vendors.
Except for specific details, the 50% solids styrene-butadiene latex (TC-S110) and the 45% solids nitrile latex (TC-N230R) of the following examples were purchased from Zhejiang morning rubber, inc., and the 40% solids styrene-butadiene latex (980) was purchased from Zibologut technology, inc.; the hydrogenation catalyst Grubbs 2 was purchased from Jiangsu Xinnoco catalyst Co., ltd. Model SC-1002. 1L microreactors were purchased from da Lian MicroKai chemical Co. The parts are all parts by mass.
Example 1
(1) Solution configuration
2 Parts by weight of a hydrogenation catalyst Grubbs2 and 1 part by weight of sodium dodecylbenzenesulfonate as an emulsifier were dissolved in a mixture of 100 parts by weight of water/methylene chloride (90 parts by weight of water, 10 parts by weight of methylene chloride) and stirred under a nitrogen atmosphere to dissolve and emulsify the hydrogenation catalyst, thereby obtaining a solution A.
(2) Hydrogenation reaction
The temperature of the microreactor system is regulated to 80 ℃, and then the air in the microreactor pipeline is discharged by nitrogen. 1000 parts of styrene-butadiene latex (solid content of 50%) is controlled to flow at 100mL/min and solution A is controlled to flow at 10mL/min through two metering pumps, and the mixture is pumped into a microreactor with 1L capacity to carry out continuous reaction, and the reaction pressure of a system in the microreactor is controlled to be 4MPa, and after about 9min, hydrogenated conjugated diene latex is obtained at the outlet of the tail end of the microreactor. And then removing excessive methylene dichloride under reduced pressure to obtain hydrogenated latex.
Examples 2 to 7 and comparative examples 1 to 4
With reference to the conditions of example 1, the hydrogenation reaction of the conjugated diene latex was carried out, with other conditions maintained, according to the process parameters shown in Table 1, to prepare the corresponding hydrogenated latex.
TABLE 1 Process parameters for the hydrogenation reactions in examples 1-7 and comparative examples 1-4
Effect example 1
The following performance tests were carried out on the hydrogenated latices obtained in examples 1 to 7 and comparative examples 1 to 4, respectively, and the latices before hydrogenation:
(1) Determination of the degree of hydrogenation:
the degree of hydrogenation was calculated based on IR spectroscopy.
The degree of hydrogenation of the hydrogenated styrene-butadiene latex was measured by referring to the method of CN 114965345A. For styrene-butadiene latex, the 699cm -1 is the characteristic absorption peak of benzene ring; the characteristic peaks of cis-1, 4-structure, 1, 2-structure and trans-1, 4-structure of the polybutadiene block are respectively at 758cm -1,911cm-1,966cm-1. As shown in FIG. 1, the infrared spectrum of the styrene-butadiene latex (SBR) of example 1 before and after hydrogenation is compared, wherein HSBR is hydrogenated styrene-butadiene latex.
The degree of hydrogenation of the hydrogenated nitrile latex was measured by the SH/T1762-2008 method. For nitrile latex, the characteristic peaks at 2236cm -1、970cm-1 and 723cm -1 are of major concern. Wherein the 2236cm -1 peak was designated cyano (c≡n), the 970cm -1 peak was designated c=c (1, 4-trans), and the 723cm -1 peak was designated as the new peak of (CH 2)n (N > 4).
(2) The mechanical properties (tensile strength, elongation at break, 300% tensile stress) were determined with reference to GB/T528 2009.
The test results obtained are shown in Table 2.
TABLE 2 Performance parameters of the hydrogenated latices obtained in examples 1-7 and comparative examples 1-4 and the latices before hydrogenation
As can be seen from examples 1 to 7 and comparative examples 1 to 6, hydrogenated styrene-butadiene/acrylonitrile-butadiene rubber latices with a higher degree of hydrogenation and significantly enhanced mechanical properties (tensile strength, elongation at break, 300% elongation stress) can be obtained by the preparation method of the present invention. Among these, in comparative examples 1 to 6, the hydrogenation catalyst of comparative example 1 was added in a small proportion, resulting in insufficient reaction and low hydrogenation degree; the comparative example 2 has a small addition ratio of the emulsifier, which results in insufficient reaction and low hydrogenation degree because the hydrogenation catalyst is not completely dissolved in the solution a; comparative examples 3 and 4 were low in temperature and pressure, reduced in reaction rate, and low in hydrogenation degree of the obtained latex, resulting in failure to greatly improve mechanical properties; comparative example 5 has a flow rate ratio too high, insufficient reaction, and low hydrogenation degree; in comparative example 6, the equivalent diameter of the channel is too large, so that the reaction process is heated unevenly, and the hydrogenation effect is poor.
Claims (10)
1. A process for preparing a hydrogenated latex, comprising the steps of: pumping solution A and latex into a micro-reactor respectively for continuous reaction to obtain hydrogenated latex; wherein,
The solution A comprises a hydrogenation catalyst, an emulsifier and a solvent;
The latex is an emulsion comprising an unsaturated rubber;
The mass ratio of the hydrogenation catalyst to the unsaturated rubber is not less than 0.4%;
The mass ratio of the emulsifier to the unsaturated rubber is not less than 0.2%;
the temperature of the continuous reaction is not lower than 50 ℃, and the pressure is not lower than 2MPa;
The equivalent diameter of the channel in the microreactor is not higher than 4mm;
The flow rate ratio of the latex to the solution A pumped into the microreactor is not higher than 30:1.
2. The method for preparing hydrogenated latex according to claim 1, wherein the structural formula of the hydrogenated latex comprises fragments represented by formula 1 and/or formula 2:
wherein a, b, c, d, e, f, g, h and i are both degrees of polymerization, each independently is an integer greater than or equal to 1.
3. The process for preparing a hydrogenated latex according to claim 2, wherein the hydrogenated latex has a degree of hydrogenation of not less than 90%, preferably not less than 95%;
And/or the tensile strength of the hydrogenated latex is not lower than 20MPa, preferably 20-30MPa;
And/or the elongation at break of the hydrogenated latex is not higher than 400%, preferably 350% -400%;
And/or the hydrogenated latex has a 300% elongation stress of not less than 3MPa, preferably 3 to 4MPa.
4. The process for the preparation of a hydrogenated latex according to claim 1, characterized in that the mass ratio of the hydrogenation catalyst to the unsaturated rubber is comprised between 0.4% and 8%, preferably between 2% and 8%, more preferably between 2% and 5%;
and/or the mass ratio of the surfactant to the unsaturated rubber is 0.2% -5.5%, preferably 0.5% -5.5%, more preferably 1% -2%;
and/or the temperature of the continuous reaction is 50 ℃ to 150 ℃, preferably 80 ℃ to 100 ℃;
And/or the pressure of the continuous reaction is 2-10MPa, preferably 3-6MPa.
5. The process for the preparation of hydrogenated latices according to claim 1, wherein the equivalent diameter of the channels in the microreactor is lower than 3mm;
And/or the flow rate of the latex pumped into the microreactor is 10-500mL/min, preferably 50-300mL/min;
And/or the flow rate of the solution A pumped into the microreactor is 10-100mL/min, preferably 10-50mL/min;
and/or the ratio of the flow rates of the latex and the solution A pumped into the microreactor is (1-30): 1, preferably (10-20): 1.
6. A process for the preparation of a hydrogenated latex according to claim 1, wherein the solids content of the unsaturated rubber in the latex is lower than 55%, preferably between 40% and 50%, said percentages being by mass;
And/or the unsaturated rubber is a rubber containing unsaturated carbon-carbon double bonds, preferably a conjugated diene polymer rubber, more preferably one or more selected from natural rubber, polybutadiene, polyisoprene, a styrene-butadiene copolymer, an acrylonitrile-butadiene copolymer, butadiene-isoprene, a butadiene-acrylonitrile-butyl acrylate terpolymer and a butadiene-acrylonitrile-acrylic acid terpolymer, still more preferably a styrene-butadiene copolymer and/or an acrylonitrile-butadiene copolymer;
and/or the emulsifier is selected from one or more of amphoteric betaines, cationic surfactants, anionic surfactants, and nonionic surfactants; the amphoteric betaine is preferably selected from one or more of 3-N, N (dimethyldodecylamino) -propane sulfonate, tetradecylamide propyl hydroxypropyl sulfobetaine and decane-dimethyl hydroxypropyl sulfobetaine; the cationic surfactant is preferably selected from cetyl dimethyl ammonium chloride and/or stearyl trimethyl ammonium chloride; the anionic surfactant is preferably selected from one or more of sodium dodecyl sulfate, sodium fatty alcohol polyoxyethylene ether sulfate and sodium lauryl sulfate; the nonionic surfactant is preferably selected from fatty alcohol polyoxyethylene ether and/or alkylphenol polyoxyethylene ether;
and/or, the structural formula of the hydrogenation catalyst is shown as formula 3 or formula 4:
wherein M is preferably a group VIII metal element, more preferably ruthenium or osmium;
And/or, the X 1、X2 are each independently selected from an anionic ligand, preferably selected from one of Cl, CF 3COO、CH3 COO, tosylate, (CF 3)(CH3)2 CO, phenoxy, CFH 2COO、(CH3)3 CO, methoxy, ethoxy, mesylate and triflate;
and/or, L is an uncharged electron donor, and the structural formula of L is preferably shown as formula 5:
And/or, the R 1 is selected from one of hydrogen, alkyl, alkenyl, alkynyl and aryl;
And/or, each of the R 2、R3、R4 and R 5 is independently selected from one of hydrogen, halogen, nitro, CF 3、C1-C30 alkyl, C 3-C20 alkynyloxy, C 2-C20 alkenyl, C 2-C20 alkynyl, C 6-C24 aryl, C 1-C20 alkoxy, C 2-C20 alkenyloxy, C 2-C20 alkynyloxy, C 6-C24 aryloxy, C 2-C20 alkoxycarbonyl, C 1-C20 alkylamino, C 1-C20 alkylthio, C 6-C24 arylthio, C 1-C20 alkylsulfonyl, and C 1-C20 alkylsulfinyl;
And/or, Y is selected from one of O, S, N and P groups;
And/or, each of R 6、R7 and R 8 is independently selected from one or more of alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl and alkylsulfinyl;
More preferably, the structural formula of the dehydrogenation catalyst is shown in formula 6 or formula 7:
7. The process for the preparation of a hydrogenated latex according to claim 1, wherein said continuous reaction is carried out under an inert atmosphere;
and/or the solvent is water and dichloromethane, preferably 9:1 by weight;
and/or, after the end of the continuous reaction, a step of removing the solvent, preferably under reduced pressure, is further included.
8. Hydrogenated latex, characterized in that it is produced according to the process for the preparation of hydrogenated latices according to any one of claims 1 to 7.
9. Use of the hydrogenated latex according to claim 8 in the field of automotive manufacture, in the field of wire and cable or in the field of medical devices.
10. The use according to claim 9, wherein said application in the field of automotive manufacture comprises the production of automotive tires from said hydrogenated latex;
And/or, the application in the wire and cable field includes using the hydrogenated latex as a coating material for wires and cables;
And/or applications in the medical device field include producing surgical devices, infusion sets, syringes or medical bandages from the hydrogenated latex.
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