CN114479086A - Viscosity-adjustable methyl modified polysiloxane and preparation method thereof - Google Patents
Viscosity-adjustable methyl modified polysiloxane and preparation method thereof Download PDFInfo
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- modified polysiloxane
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 53
- -1 polysiloxane Polymers 0.000 title claims abstract description 42
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004793 Polystyrene Substances 0.000 claims abstract description 51
- 229920002223 polystyrene Polymers 0.000 claims abstract description 51
- 239000004005 microsphere Substances 0.000 claims abstract description 50
- 229920002545 silicone oil Polymers 0.000 claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 46
- 239000001257 hydrogen Substances 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims abstract description 11
- ACXIAEKDVUJRSK-UHFFFAOYSA-N methyl(silyloxy)silane Chemical compound C[SiH2]O[SiH3] ACXIAEKDVUJRSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 21
- 150000002431 hydrogen Chemical class 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 150000008064 anhydrides Chemical class 0.000 claims description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229960003080 taurine Drugs 0.000 claims description 8
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 7
- 229960001701 chloroform Drugs 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- 229940044603 styrene Drugs 0.000 claims description 2
- 229940095068 tetradecene Drugs 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 2
- 239000002210 silicon-based material Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920005990 polystyrene resin Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 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 description 2
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004590 silicone sealant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a viscosity-adjustable methyl modified polysiloxane and a preparation method thereof, and relates to the technical field of organic silicon materials. The methyl modified polysiloxane with adjustable viscosity is prepared by taking methyl high hydrogen silicone oil, octamethylcyclotetrasiloxane and methyldisiloxane as raw materials and sequentially carrying out telomerization, neutralization, filtration, hydrosilylation and reduction on the raw materials, and has the advantages of simple and convenient operation of the preparation method and yield of more than 95%. The sulfonic polystyrene gel exchange resin is obtained by modifying the polystyrene microspheres, and sulfonic acid groups are grafted on the surfaces of the polystyrene microspheres through fatty chains, so that the thermal stability of the catalyst is improved.
Description
Technical Field
The invention relates to the technical field of organic silicon materials, in particular to methyl modified polysiloxane with adjustable viscosity and a preparation method thereof.
Background
The organic silicon is a novel high polymer material, has excellent weather resistance, good extensibility and stable ultraviolet resistance, and is widely applied to the fields of military industry, civil use, aerospace, ocean, building manufacturing and the like. The methyl hydrogen-containing silicone oil is mainly applied to a cross-linking agent, a defoaming agent, a release agent, an isolating agent and the like of addition type liquid silicone rubber, and the consumption of the fields is small, so that the excess of the productivity of a large amount of hydrogen-containing silicone oil is caused. The methyl modified polysiloxane resin with adjustable viscosity, which is prepared by using methyl hydrogen-containing silicone oil as a raw material, is an application field for optimizing products in the industry and expanding methyl high hydrogen-containing silicone oil.
The synthesis method of the low hydrogen-containing silicone oil mainly comprises three methods: one is the halosilane process: using methyl hydrogen dichlorosilane, dimethyl dichlorosilane and trimethyl chlorosilane as raw materials, using concentrated sulfuric acid or strong acid cation resin as a catalyst, and obtaining a finished product through hydrolytic decomposition and low-pressure reduction; secondly, ring-opening copolymerization: the method comprises the following steps of (1) utilizing octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane to carry out ring-opening copolymerization, and taking sulfuric acid, p-toluenesulfonic acid or acidic clay as a catalyst in a nitrogen atmosphere to prepare low-hydrogen silicone oil; and thirdly, a high hydrogen-containing silicone oil telomerization method, namely preparing the low hydrogen silicone oil by using trimethyl silicon terminated high hydrogen-containing silicone oil, octamethylcyclotetrasiloxane and hexamethyldisiloxane as raw materials and using sulfuric acid, trifluoromethanesulfonic acid or strong acid cation resin as a catalyst. The telomerization method of the high hydrogen-containing silicone oil has the advantages of mild reaction conditions, simple reaction process and the like, so that the method is a common method in the low hydrogen silicone oil manufacturing industry in China. The low-hydrogen silicone oil prepared by using the strong-acid cation resin as the catalyst has the advantages of easiness in separation and recovery, higher product purity compared with a product obtained by homogeneous catalytic reaction, small corrosion to production equipment and the like. However, the traditional sulfonic cation exchange resin is prepared and synthesized by methods such as concentrated sulfuric acid, fuming sulfuric acid method, gaseous or liquid sulfur trioxide method and the like, as shown in fig. 1, the sulfonic cation exchange resin is directly sulfonated on benzene rings of polystyrene resin, and the obtained sulfonic group has poor thermal stability, low degree of freedom, difficult exchange with cations of other macromolecules and high catalyst activation difficulty.
Disclosure of Invention
The invention aims to provide a viscosity-adjustable methyl modified polysiloxane and a preparation method thereof, and solves the following technical problems:
the sulfonic acid group of the prior sulfonic acid group cation exchange resin is directly connected with the benzene ring of the polystyrene resin, so that the thermal stability of the sulfonic acid group is poor, and the prepared sulfonic acid group cation resin has high sulfonation reverse reaction difficulty.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of viscosity-adjustable methyl modified polysiloxane comprises the following steps:
injecting methyl high hydrogen-containing silicone oil, octamethylcyclotetrasiloxane and methyldisiloxane into a reaction kettle, heating the reaction kettle to 20-60 ℃, and performing telomerization, neutralization and filtration to obtain methyl low hydrogen-containing silicone oil;
step two, reacting the methyl low-hydrogen silicone oil prepared in the step one with olefin under the condition of a catalyst to obtain a silicone oil mixture;
and step three, separating and purifying the silicone oil mixture, reducing pressure and removing low boiling point substances, wherein the temperature is 150-200 ℃, the vacuum degree is-0.10 to-0.085 MPa, and the removing time is 1.5-3.5 hours, so as to obtain the methyl modified polysiloxane.
As a further scheme of the invention: the mass percentage content of hydrogen in the methyl high hydrogen-containing silicone oil is 0.36-1.62%.
As a further scheme of the invention: the olefin is any one of ethylene, propylene, butene, pentene, hexene, octene, decene, dodecene, tetradecene, styrene, isobornene, acrylate, methacrylate and vinyl acetate, and the mass ratio of the low-hydrogen silicone oil to the olefin is 100: 40-160.
As a further scheme of the invention: the viscosity of the methyl modified polysiloxane is 300-80000 mm2/s。
As a further scheme of the invention: the preparation method of the catalyst comprises the following steps:
(1) preparing anhydride modified polystyrene microspheres: adding polystyrene microspheres, trichloromethane and N, N-dimethylformamide into a reaction bottle, mechanically stirring uniformly, standing for 6-12 h, adding 1,2, 4-trimellitic anhydride acyl chloride, mechanically stirring uniformly, adding stannic chloride, reacting for 3-6 h at normal temperature, carrying out reduced pressure suction filtration, washing with diethyl ether, and drying in vacuum to obtain anhydride modified polystyrene microspheres;
(2) preparing carboxyl modified polystyrene microspheres: washing the anhydride modified polystyrene microspheres with deionized water, washing with 0.1-0.5 mol/L sodium hydroxide aqueous solution, washing with deionized water, and vacuum drying to obtain carboxyl modified polystyrene microspheres;
(3) preparing a catalyst: adding the carboxyl modified polystyrene microspheres and N, N-dimethylformamide into a reaction bottle, mechanically stirring uniformly, adding 2-aminoethanesulfonic acid, sodium hydroxide and deionized water, and reacting at room temperature for 2-4h to obtain the catalyst.
As a further scheme of the invention: in the step (1), the mass ratio of the polystyrene microspheres, the trichloromethane, the N, N-dimethylformamide, the 1,2, 4-trimellitic anhydride chloride and the stannic chloride is 100: 5000-8000: 1000-2000: 200-450: 450 to 700.
As a further scheme of the invention: in the step (3), the mass ratio of the carboxyl modified polystyrene microspheres to the N, N-dimethylformamide to the 2-aminoethanesulfonic acid to the sodium hydroxide to the deionized water is 100: 800-1500: 40-65: 20-35: 250 to 400.
As a further scheme of the invention: the viscosity-adjustable methyl modified polysiloxane is prepared by any one of the preparation methods.
As a further scheme of the invention: the weight parts of the components are 30-80 parts of methyl high hydrogen silicone oil, 10-50 parts of octamethylcyclotetrasiloxane and 5-15 parts of methyl disiloxane.
The invention has the beneficial effects that:
(1) the method comprises the steps of taking polystyrene microspheres and 1,2, 4-trimellitic anhydride acyl chloride as raw materials, taking stannic chloride as a catalyst, carrying out Friedel-Crafts reaction on benzene rings on the polystyrene microspheres and acyl chloride groups of 1,2, 4-trimellitic anhydride acyl chloride molecules, bonding the anhydride groups to the surfaces of the polystyrene microspheres to obtain anhydride modified polystyrene microspheres, and sequentially washing the obtained anhydride modified polystyrene microspheres with water, alkali and water to obtain carboxylated modified polystyrene microspheres; and finally, reacting carboxyl grafted on the carboxylated modified polystyrene microsphere with amino of 2-aminoethanesulfonic acid, and grafting a large amount of sulfuric acid groups on the polystyrene microsphere to obtain the catalyst. According to the invention, a sulfonic acid group is grafted on the surface of the polystyrene microsphere through a series of reactions, and the sulfonic acid group is bonded with the polystyrene resin through a fatty carbon chain, so that the sulfonic acid group is prevented from being directly grafted on a benzene ring group on the polystyrene resin, the steric hindrance is small, the catalytic reaction is easy to participate, and the thermal stability of the grafting of the sulfonic acid group and the polymer is effectively improved.
(2) The methyl modified polysiloxane with adjustable viscosity is prepared by taking methyl high hydrogen silicone oil, octamethylcyclotetrasiloxane and methyldisiloxane as raw materials and a catalyst as a catalyst through telomerization, neutralization, filtration, hydrosilylation and reduction sequentially, and the viscosity of the obtained methyl modified polysiloxane with adjustable viscosity is 300-80000 mm2The methyl hydrogen-containing silicone oil/s can be used as a silicone sealant plasticizer, a powder surface treatment agent and a silicone adhesive color paste pigment, has a wide application field, improves the added value of methyl hydrogen-containing silicone oil, and has the advantages of simple and convenient preparation method operation and yield of more than 95 percent.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a prior art sulfonic acid group cation exchange resin formula;
FIG. 2 is a reaction scheme of the synthesis catalyst of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
referring to fig. 2, the preparation method of the catalyst includes the following steps:
(1) preparing anhydride modified polystyrene microspheres: adding 7.5g of polystyrene microspheres, 375g of trichloromethane and 80mL of N, N-dimethylformamide into a reaction bottle, mechanically stirring uniformly, standing for 6h, adding 15g of 1,2, 4-trimellitic anhydride acyl chloride, mechanically stirring uniformly, adding 34.5g of stannic chloride, reacting for 3h under the condition of normal temperature, carrying out reduced pressure suction filtration, washing with diethyl ether, and drying in vacuum to obtain anhydride modified polystyrene microspheres;
(2) preparing carboxyl modified polystyrene microspheres: washing anhydride modified polystyrene microspheres with deionized water, washing with 0.1mol/L sodium hydroxide aqueous solution, washing with deionized water, and vacuum drying to obtain carboxyl modified polystyrene microspheres;
(3) preparing a catalyst: adding 5g of carboxyl modified polystyrene microspheres and 40mL of N, N-dimethylformamide into a reaction bottle, mechanically stirring uniformly, adding 2g of 2-aminoethanesulfonic acid, 1g of sodium hydroxide and 12.5mL of deionized water, and reacting at room temperature for 2h to obtain the catalyst.
Example 2:
referring to fig. 2, the preparation method of the catalyst includes the following steps:
(1) preparing anhydride modified polystyrene microspheres: adding 7.5g of polystyrene microspheres, 525g of trichloromethane and 120mL of N, N-dimethylformamide into a reaction bottle, mechanically stirring uniformly, standing for 9h, adding 26.5g of 1,2, 4-trimellitic anhydride acyl chloride, mechanically stirring uniformly, adding 37.5g of stannic chloride, reacting for 4.5h at normal temperature, carrying out reduced pressure suction filtration, washing with diethyl ether, and drying in vacuum to obtain anhydride modified polystyrene microspheres;
(2) preparing carboxyl modified polystyrene microspheres: washing anhydride modified polystyrene microspheres with deionized water, washing with 0.3mol/L sodium hydroxide aqueous solution, washing with deionized water, and vacuum drying to obtain carboxyl modified polystyrene microspheres;
(3) preparing a catalyst: adding 5g of carboxyl modified polystyrene microspheres and 60mL of N, N-dimethylformamide into a reaction bottle, mechanically stirring uniformly, adding 2.5g of 2-aminoethanesulfonic acid, 1.5g of sodium hydroxide and 17.5mL of deionized water, and reacting at room temperature for 3h to obtain the catalyst.
Example 3:
referring to fig. 2, the preparation method of the catalyst includes the following steps:
(1) preparing anhydride modified polystyrene microspheres: adding 7.5g of polystyrene microspheres, 600g of trichloromethane and 155mL of N, N-dimethylformamide into a reaction bottle, mechanically stirring uniformly, standing for 12h, adding 33.75g of 1,2, 4-trimellitic anhydride acyl chloride, mechanically stirring uniformly, adding 52.5g of stannic chloride, reacting for 6h at normal temperature, carrying out reduced pressure suction filtration, washing with diethyl ether, and drying in vacuum to obtain anhydride modified polystyrene microspheres;
(2) preparing carboxyl modified polystyrene microspheres: washing anhydride modified polystyrene microspheres with deionized water, washing with 0.5mol/L sodium hydroxide aqueous solution, washing with deionized water, and vacuum drying to obtain carboxyl modified polystyrene microspheres;
(3) preparing a catalyst: adding 5g of carboxyl modified polystyrene microspheres and 75mL of N, N-dimethylformamide into a reaction bottle, mechanically stirring uniformly, adding 3.2g of 2-aminoethanesulfonic acid, 1.7g of sodium hydroxide and 20mL of deionized water, and reacting at room temperature for 4h to obtain the catalyst.
Example 4:
a preparation method of viscosity-adjustable methyl modified polysiloxane comprises the following steps:
step one, injecting 20g of methyl high hydrogen silicone oil, 6.8g of octamethylcyclotetrasiloxane and 3.5g of methyl disiloxane into a reaction kettle, wherein the mass percent of hydrogen in the methyl high hydrogen silicone oil is 0.36%, heating the reaction kettle to 20 ℃, and performing telomerization, neutralization and filtration to obtain the methyl low hydrogen silicone oil.
Step two, reacting 18g of methyl low hydrogen silicone oil prepared in step one with 7.2g of ethylene under the condition of the catalyst prepared in the embodiment 1 to obtain a silicone oil mixture;
and step three, separating and purifying the silicone oil mixture, reducing the pressure and removing the low boiling point substances, wherein the temperature of the process of removing the low boiling point substances is 150 ℃, the vacuum degree is-0.10 MPa, and the removing time is 1.5h to obtain the methyl modified polysiloxane, and the yield of the methyl modified polysiloxane is 95.41%.
Example 5:
a preparation method of viscosity-adjustable methyl modified polysiloxane comprises the following steps:
step one, injecting 30g of methyl high hydrogen silicone oil, 15g of octamethylcyclotetrasiloxane and 5g of methyl disiloxane into a reaction kettle, wherein the mass percentage of hydrogen in the methyl high hydrogen silicone oil is 1.12%, heating the reaction kettle to 40 ℃, and performing telomerization, neutralization and filtration to obtain the methyl low hydrogen silicone oil.
Step two, reacting 15g of methyl low hydrogen silicone oil prepared in step one with 15g of ethylene under the condition of the catalyst prepared in the embodiment 1 to obtain a silicone oil mixture;
and step three, separating and purifying the silicone oil mixture, reducing the pressure and removing the low boiling point substances, wherein the temperature of the process of removing the low boiling point substances is 180 ℃, the vacuum degree is-0.09 MPa, and the removing time is 2.5 hours, so that the methyl modified polysiloxane is obtained, and the yield of the methyl modified polysiloxane is 97.32%.
Example 6:
a preparation method of viscosity-adjustable methyl modified polysiloxane comprises the following steps:
step one, injecting 20g of methyl high hydrogen silicone oil, 12.5g of octamethylcyclotetrasiloxane and 3.7g of methyl disiloxane into a reaction kettle, wherein the mass percent of hydrogen in the methyl high hydrogen silicone oil is 1.62%, heating the reaction kettle to 60 ℃, and performing telomerization, neutralization and filtration to obtain the methyl low hydrogen silicone oil.
Step two, reacting 15g of methyl low hydrogen silicone oil prepared in step one with 24g of ethylene under the condition of the catalyst prepared in the embodiment 1 to obtain a silicone oil mixture;
and step three, separating and purifying the silicone oil mixture, reducing the pressure and removing the low boiling point substances, wherein the temperature of the process of removing the low boiling point substances is 200 ℃, the vacuum degree is-0.085 MPa, the removing time is 3.5 hours, the methyl modified polysiloxane is obtained, and the yield of the methyl modified polysiloxane is 96.11%.
Comparative example 1:
a preparation method of viscosity-adjustable methyl modified polysiloxane comprises the following steps:
compared with example 4, the catalyst prepared in example 1 was replaced with NKC-9 resin catalyst manufactured and sold by Tianjin Nankai and science and technology Co. The other preparation methods were the same as in example 4, and the yield of the methyl-modified polysiloxane was 89.33%.
While one embodiment of the present invention has been described in detail, the description is only a preferred embodiment of the present invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (9)
1. The preparation method of the viscosity-adjustable methyl modified polysiloxane is characterized by comprising the following steps of:
injecting methyl high hydrogen-containing silicone oil, octamethylcyclotetrasiloxane and methyldisiloxane into a reaction kettle, heating the reaction kettle to 20-60 ℃, and performing telomerization, neutralization and filtration to obtain methyl low hydrogen-containing silicone oil;
step two, reacting the methyl low-hydrogen silicone oil prepared in the step one with olefin under the condition of a catalyst to obtain a silicone oil mixture;
and step three, separating and purifying the silicone oil mixture, reducing pressure and removing low boiling point substances, wherein the temperature is 150-200 ℃, the vacuum degree is-0.10 to-0.085 MPa, and the removing time is 1.5-3.5 hours, so as to obtain the methyl modified polysiloxane.
2. The method for preparing the methyl modified polysiloxane with adjustable viscosity according to claim 1, wherein the hydrogen content in the methyl high hydrogen silicone oil is 0.36-1.62% by mass.
3. The method for preparing the viscosity-adjustable methyl-modified polysiloxane according to claim 1, wherein the olefin is any one of ethylene, propylene, butene, pentene, hexene, octene, decene, dodecene, tetradecene, styrene, isobornene, acrylate, methacrylate and vinyl acetate, and the mass ratio of the low-hydrogen silicone oil to the olefin is 100: 40-160.
4. The method for preparing the viscosity-adjustable methyl-modified polysiloxane according to claim 1,the viscosity of the methyl modified polysiloxane is 300-80000 mm2/s。
5. The method for preparing the viscosity-adjustable methyl-modified polysiloxane according to claim 1, wherein the method for preparing the catalyst comprises the following steps:
(1) preparing anhydride modified polystyrene microspheres: adding polystyrene microspheres, trichloromethane and N, N-dimethylformamide into a reaction bottle, mechanically stirring uniformly, standing for 6-12 h, adding 1,2, 4-trimellitic anhydride acyl chloride, mechanically stirring uniformly, adding stannic chloride, reacting for 3-6 h at normal temperature, carrying out reduced pressure suction filtration, washing with diethyl ether, and drying in vacuum to obtain anhydride modified polystyrene microspheres;
(2) preparing carboxyl modified polystyrene microspheres: washing the anhydride modified polystyrene microspheres with deionized water, washing with 0.1-0.5 mol/L sodium hydroxide aqueous solution, washing with deionized water, and vacuum drying to obtain carboxyl modified polystyrene microspheres;
(3) preparing a catalyst: adding the carboxyl modified polystyrene microspheres and N, N-dimethylformamide into a reaction bottle, mechanically stirring uniformly, adding 2-aminoethanesulfonic acid, sodium hydroxide and deionized water, and reacting at room temperature for 2-4h to obtain the catalyst.
6. The method for preparing the viscosity-adjustable methyl-modified polysiloxane according to claim 5, wherein the method comprises the following steps: in the step (1), the mass ratio of the polystyrene microspheres, the trichloromethane, the N, N-dimethylformamide, the 1,2, 4-trimellitic anhydride chloride and the stannic chloride is 100: 5000-8000: 1000-2000: 200-450: 450 to 700.
7. The method for preparing the viscosity-adjustable methyl-modified polysiloxane according to claim 5, wherein the method comprises the following steps: in the step (3), the mass ratio of the carboxyl modified polystyrene microspheres to the N, N-dimethylformamide to the 2-aminoethanesulfonic acid to the sodium hydroxide to the deionized water is 100: 800-1500: 40-65: 20-35: 250 to 400.
8. A viscosity-adjustable methyl-modified polysiloxane prepared by the preparation method of any one of claims 1 to 7.
9. The viscosity-adjustable methyl-modified polysiloxane according to claim 8, wherein: the weight parts of the components are 30-80 parts of methyl high hydrogen silicone oil, 10-50 parts of octamethylcyclotetrasiloxane and 5-15 parts of methyl disiloxane.
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| CN116284790A (en) * | 2023-03-27 | 2023-06-23 | 湖北兴瑞硅材料有限公司 | Acrylic ester modified silicone oil, preparation method thereof and packaging adhesive containing acrylic ester modified silicone oil |
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