CN118027411A - Synthesis method of solvent-free hyperbranched silicone resin - Google Patents
Synthesis method of solvent-free hyperbranched silicone resin Download PDFInfo
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- CN118027411A CN118027411A CN202410071510.1A CN202410071510A CN118027411A CN 118027411 A CN118027411 A CN 118027411A CN 202410071510 A CN202410071510 A CN 202410071510A CN 118027411 A CN118027411 A CN 118027411A
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- 229920002050 silicone resin Polymers 0.000 title claims description 22
- 238000001308 synthesis method Methods 0.000 title claims description 4
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 239000011347 resin Substances 0.000 claims abstract description 64
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 55
- 239000010703 silicon Substances 0.000 claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000008096 xylene Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002808 Si–O–Si Inorganic materials 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 2
- 238000001704 evaporation Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000002966 varnish Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- 239000000413 hydrolysate Substances 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 11
- 230000007935 neutral effect Effects 0.000 description 11
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 9
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000005051 trimethylchlorosilane Substances 0.000 description 9
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 5
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- -1 polysiloxanes Polymers 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- MNKYQPOFRKPUAE-UHFFFAOYSA-N chloro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 MNKYQPOFRKPUAE-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- SCOAPWHDFLOMRC-UHFFFAOYSA-N prop-2-enoic acid;trimethoxy(propyl)silane Chemical compound OC(=O)C=C.CCC[Si](OC)(OC)OC SCOAPWHDFLOMRC-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IJNRGJJYCUCFHY-UHFFFAOYSA-N ethenyl-dimethoxy-phenylsilane Chemical compound CO[Si](OC)(C=C)C1=CC=CC=C1 IJNRGJJYCUCFHY-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
The invention belongs to the technical field of organic silicon resin, and particularly discloses solvent-free hyperbranched organic silicon resin and a preparation method thereof. The solvent-free hyperbranched silicon resin is prepared from a difunctional monomer (A 2), a trifunctional monomer (B 3), a difunctional monomer (AB 2), a monofunctional monomer (C), a solvent and water by the steps of hydrolysis, prepolymerization, end-capping reaction, water washing, solvent removal and the like, wherein the viscosity of the resin is 80-2000 mPa.s (25 ℃), and the molecular weight is 1800-10000g/mol. The method has the advantages of mild reaction conditions, high yield, easy control of the conditions and the like; the synthesized solvent-free hyperbranched organic silicon resin has low cost of raw materials, simple preparation process, suitability for industrial production, no toxicity and environmental protection, and is expected to be applied to the fields of solvent-free coating, adhesive, impregnating varnish and the like.
Description
Technical Field
The invention belongs to the technical field of organic chemistry, and relates to a method for synthesizing solvent-free hyperbranched silicone resin.
Background
With the technological change in recent years, new requirements are placed on resin materials in various fields, such as ensuring low viscosity and easy processing, and simultaneously having better mechanical properties and thermal stability. Like conventional silicone resin systems, linear polysiloxanes are generally used as reactive diluents, and long chains of linear polysiloxanes tend to entangle easily, with the tendency of viscosity to increase over time. The hyperbranched organic silicon resin has a highly branched spherical structure, has high solubility, low viscosity, good fluidity at room temperature and good viscosity stability, contains little or no volatile organic solvent, and has low toxicity, environmental protection and low cost when in use.
Therefore, when the silicone resin is widely used, no solvation is more and more paid attention to in the research and development process of the resin from the aspects of safety, health, environmental protection and product performance.
Chinese patent CN116554481a discloses an organic silicon resin and its industrialized preparation method, which is mainly characterized in that: mixing an organosilicon end-capping agent, deionized water, boric acid, a cosolvent and a catalyst, heating to 40-70 ℃ under stirring, and hydrolyzing for 30-60 min to obtain a prehydrolysis product; dripping ethyl silicate into the hydrolysate to obtain a pre-polycondensation material; heating the pre-condensed material to 75-85 ℃, refluxing for 120-210 min, and cooling to 30-65 ℃ after refluxing; then adding an extractant and 0.05 to 0.5 mass part of acid binding agent while stirring, then adjusting the PH to 5 to 6, standing and separating liquid to obtain an organic phase; the organic phase is slowly heated to 85-105 ℃ while being stirred, then cooled to room temperature and filtered, and the organic silicon resin is obtained. The method solves the problems of more waste water, low yield and difficult filtration of products in the traditional organosilicon tree production process, but the solid content of the organosilicon tree is only about 50 percent, the organosilicon tree is still required to be diluted by an organic solvent, and the environment-friendly industrial production still cannot be realized.
Chinese patent CN112898574B discloses a preparation method of organic silicon resin, which is mainly characterized in that: adding cyclosiloxanes and phenylcyclosiloxanes to the reactor and heating to remove water; adding an initiator, an accelerator, a blocking agent and an anhydrous solvent into a reactor for reaction, and removing the anhydrous solvent after the reaction is finished to obtain a prepolymer containing vinyl; and adding the prepolymer, a platinum catalyst, hydrogen-containing polysiloxane and fluorine-containing allyl ether into an anhydrous solvent for reaction, and removing the solvent after the reaction is finished to obtain the organic silicon resin. The prepared organic silicon resin has good compatibility with a resin matrix and good dispersibility by adopting a step polymerization mode. Toluene is still required to be used as a solvent for diluting the organic silicon resin product, and the environment-friendly requirement is not met.
At present, the organic silicon resin in the market contains a large amount of organic solvents when in use, pollutes the environment when in use, and does not meet the requirements of environmental protection.
Aiming at the defects of the prior art, the invention provides a preparation method of solvent-free hyperbranched silicone resin. The carbon content in the resin structure is low, and the phenomenon of smoking can not occur under the high temperature condition.
Disclosure of Invention
In order to solve the technical problems, the invention provides a synthesis method of solvent-free hyperbranched silicone resin. In order to achieve the above purpose, the present invention adopts the following technical scheme:
The chemical structural formula of the solvent-free hyperbranched silicone resin is as follows:
In the middle of R1、R2、R3＝-C6H5、-(CH2)jCH3、-(CH2)kCH＝CH2、-CH2(CH2)mOCOCH＝CH2、-CH2(CH2)nOCOC(CH3)＝CH2;
Wherein R 4＝-C6H5、-(CH2)jCH3;
wherein i, j, k, m, n are each independently selected from any integer from 0 to 5.
The molecular weight of the solvent-free hyperbranched organic silicon resin is as follows: 1800-10000g/mol, viscosity of 80-2000 mPa.s at 25 ℃ and VOC content of less than 5wt%.
Preparation of solvent-free hyperbranched silicone resin:
The solvent-free hyperbranched organic silicon resin is prepared by taking a trifunctional monomer (B 3), a difunctional monomer (A 2), a difunctional monomer (AB 2) and a monofunctional monomer (C) as main raw materials.
The method comprises the following specific steps: sequentially adding an organic solvent and water into a reaction kettle with a stirrer and a condenser, heating to about 50-90 ℃, slowly dripping mixed solution of a difunctional monomer (A 2), a trifunctional monomer (B 3) and a difunctional monomer (AB 2) under stirring, and stirring and reacting for 0.5-5 hours at 50-90 ℃; then adding the monofunctional monomer (C), and continuously stirring and reacting for 0.5-3 hours at 50-90 ℃. Then washing with deionized water to neutrality, and removing the organic solvent by rotary evaporation to obtain solvent-free hyperbranched organic silicon resin; wherein the difunctional monomer (A 2) participating in the reaction has the chemical structure as follows: r 2(R3)Si(R5)2; the chemical structure of trifunctional monomer (B 3) is: r 1Si(R5)3; the chemical structure of the difunctional monomer (AB 2) is: r 1(R2)Si(R5)2. Wherein R 5 is-Cl, -O (CH 2)iCH3. Monofunctional monomer (C) is one or more of (CH3)3SiCl、(C2H5)3SiCl、(C6H5)3SiCl、(CH3)3SiOCH3、(C2H5)3SiOC2H5、(CH3)3Si-O-Si(CH3)3、(CH3)3Si-O-Si(C2H5)3、(C2H5)3Si-O-Si(C2H5)3.
The molar ratio of the difunctional monomer (A 2), the trifunctional monomer (B 3), the difunctional monomer (AB 2) and the monofunctional monomer (C) is as follows: 1:0.7-1.5:0-0.5:0.7-1.8, and in the same reaction system, the hydrolysis groups (such as-Cl, -OCH 3、-OC2H5) of the difunctional monomer (A 2) and the trifunctional monomer (B 3) cannot be the same. The solvent required by the reaction is one or more of benzene, toluene, xylene, cyclohexane, ethanol, glycol, isopropanol, n-butanol, acetone and butanone, and the addition amount of the solvent is 1-10 times of the total mass of the reaction monomers. The solvent-free hyperbranched silicone resin has a molecular weight of 1800-10000g/mol, a viscosity of 80-2000 mPa.s at 25 ℃, a VOC content of less than 5.0wt%, more preferably less than 3.0wt%, even more preferably less than 2.0wt%.
Due to implementation of the technical scheme, compared with the prior art, the technical scheme of the invention has the following advantages and beneficial effects:
1. The adopted difunctional monomer (A 2) and the trifunctional monomer (B 3) have different hydrolytic groups, so that the reaction rate can be controlled, the gel effect can be effectively inhibited, the organic silicon resin with a hyperbranched topological structure can be further obtained, and the entanglement degree and viscosity of a molecular chain can be reduced;
2. The method for blocking the monofunctional monomer (C) can inhibit the hydrolysis rate and local infinite growth of the organic silicon resin, effectively control the molecular weight, reduce the viscosity of the resin and improve the stability of the resin.
3. The prepared hyperbranched organic silicon resin has the advantages of complete hydrolysis, less organic volatile matters generated during curing, and higher thermal decomposition temperature and heat resistance.
4. The prepared hyperbranched organic silicon resin has low VOC content, no organic solvent, safety and environmental protection, suitability for industrial production and good construction environment.
5. The prepared hyperbranched organic silicon resin has low viscosity, strong flowability, convenient brushing and other processes during construction.
Drawings
FIG. 1 is an infrared spectrum of the product of example 1, solvent-free hyperbranched silicone resin.
FIG. 2 TG and DTG spectra of the solvent-free hyperbranched silicone resin example 1 product.
Detailed Description
The technical solutions according to the present invention will be further described with reference to specific examples, but are not limited to these examples.
Example 1
(1) 250ML of water and 150mL of toluene were added to a three-necked flask equipped with a condenser stirrer and a thermometer, preheated at 75 ℃, added with a mixture of 0.4mol of methyltriethoxysilane, 0.4mol of dimethyldichlorosilane and 150mL of toluene through a constant pressure dropping funnel, reacted for 1.5 hours, warmed to 85 ℃ and then added with 0.28mol of trimethylchlorosilane and 50mL of toluene through the constant pressure dropping funnel again, stirred and mixed uniformly, and reacted for 1 hour.
(2) Standing for layering, separating out lower acid water, washing the upper hydrolysate to be neutral by using saturated sodium bicarbonate and distilled water to obtain hyperbranched organic silicon resin with a solvent, and removing the solvent and small molecular products of the silicon resin prepolymer at 75 ℃ by using a rotary evaporator to obtain low-viscosity solvent-free hyperbranched methyl organic silicon resin with the viscosity of: 80 mPas, VOC content: 3.7 wt.% of molecular weight: 2700g/mol.
Example 2
(1) 350ML of water and 200mL of xylene are added into a three-necked flask equipped with a condenser stirrer and a thermometer, preheated at 90 ℃, added with a mixture of 0.4mol of methyltriethoxysilane, 0.48mol of diphenyldichlorosilane, 0.12mol of methylphenyldimethoxysilane and 180mL of xylene through a constant pressure dropping funnel, reacted for 0.5h, and then added with 0.72mol of trimethylchlorosilane and 120mL of xylene through the constant pressure dropping funnel again at 90 ℃, stirred and mixed uniformly, and reacted for 0.5h.
(2) Standing for layering, separating out lower acid water, washing the upper hydrolysate to be neutral by using saturated sodium bicarbonate and distilled water to obtain hyperbranched organic silicon resin with a solvent, and removing the solvent and small molecular products of the silicon resin prepolymer at 75 ℃ by using a rotary evaporator to obtain low-viscosity solvent-free hyperbranched methyl organic silicon resin with the viscosity of: 973 mPa.s, VOC content: 1.9 wt.% of molecular weight: 4000g/mol.
Example 3
(1) 300ML of water and 200mL of xylene were added to a three-necked flask equipped with a condenser stirrer and a thermometer, preheated at 90℃and mixed with 0.2mol of phenyltriethoxysilane, 0.2mol of methyltriethoxysilane, 0.3mol of diphenyldichlorosilane, 0.3mol of dimethyldichlorosilane and 200mL of benzene via a constant pressure dropping funnel, reacted for 5 hours, and then heated to 80℃and then 0.48mol of trimethylchlorosilane and 80mL of benzene mixed solution were added via a constant pressure dropping funnel again, stirred and mixed uniformly, and reacted for 1.5 hours.
(2) Standing for layering, separating out lower acid water, washing the upper hydrolysate to be neutral by using saturated sodium bicarbonate and distilled water to obtain hyperbranched organic silicon resin with a solvent, and removing the solvent and small molecular products of the silicon resin prepolymer at 75 ℃ by using a rotary evaporator to obtain low-viscosity solvent-free hyperbranched methyl organic silicon resin with the viscosity of: 1247 mPa.s, VOC content: 2.4 wt.% of molecular weight: 4200g/mol.
Example 4
(1) 250ML of water and 150mL of isopropanol were added to a three-necked flask equipped with a condenser stirrer and a thermometer, preheated at 70 ℃, added with a mixture of 0.4mol of vinyltriethoxysilane, 0.14mol of dimethyldichlorosilane, 0.14mol of diphenyldichlorosilane, 0.1mol of methylphenyldimethoxysilane and 120mL of isopropanol via a constant pressure dropping funnel, reacted for 2 hours, warmed to 80 ℃, added with 0.4mol of triphenylchlorosilane via a constant pressure dropping funnel again, and mixed with 70mL of isopropanol via a constant pressure dropping funnel, stirred and mixed uniformly, and reacted for 1 hour.
(2) Standing for layering, separating out lower acid water, washing the upper hydrolysate to be neutral by using saturated sodium bicarbonate and distilled water to obtain hyperbranched organic silicon resin with a solvent, and removing the solvent and small molecular products of the silicon resin prepolymer at 75 ℃ by using a rotary evaporator to obtain low-viscosity solvent-free hyperbranched methyl organic silicon resin with the viscosity of: 784 mpa.s, VOC content: 4.1 wt.% of molecular weight: 4100g/mol.
Example 5
(1) 300ML of water and 200mL of isopropyl alcohol were added to a three-necked flask equipped with a condenser stirrer and a thermometer, preheated at 55℃and a mixture of 0.2mol of vinyltriethoxysilane, 0.2mol of methyltriethoxysilane, 0.14mol of dimethyldichlorosilane, 0.14mol of diphenyldichlorosilane, 0.1mol of methylvinyldimethoxysilane and 150mL of isopropyl alcohol was added through a constant pressure dropping funnel, reacted for 3 hours, and then heated to 65℃and then 0.4mol of trimethylchlorosilane and 70mL of isopropyl alcohol were added through a constant pressure dropping funnel, and the mixture was stirred and mixed uniformly to react for 2.5 hours.
(2) Standing for layering, separating out lower acid water, washing the upper hydrolysate to be neutral by using saturated sodium bicarbonate and distilled water to obtain hyperbranched organic silicon resin with a solvent, and removing the solvent and small molecular products of the silicon resin prepolymer at 75 ℃ by using a rotary evaporator to obtain low-viscosity solvent-free hyperbranched methyl organic silicon resin with the viscosity of: 1023 mPas, and the VOC content is as follows: 2.6 wt.% of molecular weight: 5500g/mol
Example 6
(1) 290ML of water and 190mL of cyclohexane were added to a three-necked flask equipped with a condenser stirrer and a thermometer, preheated at 55℃and mixed with 0.2mol of vinyltriethoxysilane, 0.2mol of phenyltriethoxysilane, 0.3mol of dimethyldichlorosilane, 0.22mol of diphenyldichlorosilane, 0.2mol of phenylvinyldimethoxysilane and 160mL of cyclohexane via a constant pressure dropping funnel, reacted for 3 hours, and then heated to 90℃and then 0.28mol of trimethylchlorosilane and 50mL of cyclohexane mixed solution were added via a constant pressure dropping funnel, and the mixture was stirred and mixed uniformly to react for 1 hour.
(2) Standing for layering, separating out lower acid water, washing the upper hydrolysate to be neutral by using saturated sodium bicarbonate and distilled water to obtain hyperbranched organic silicon resin with a solvent, and removing the solvent and small molecular products of the silicon resin prepolymer at 75 ℃ by using a rotary evaporator to obtain low-viscosity solvent-free hyperbranched methyl organic silicon resin with the viscosity of: 1361 mPas, VOC content is: 2.9 wt.% of molecular weight: 5300g/mol.
Example 7
(1) 250ML of water and 180mL of toluene were added to a three-necked flask equipped with a condenser stirrer and a thermometer, preheated at 70 ℃, added with a mixture of 0.2mol of methyltrimethoxysilane, 0.2mol of methyltrichlorosilane, 0.32mol of dimethyldichlorosilane, 0.08mol of methylphenyldimethoxysilane and 150mL of toluene through a constant pressure dropping funnel, reacted for 2 hours, warmed to 75 ℃, added with 0.32mol of triphenylchlorosilane again through a constant pressure dropping funnel, and mixed with 70mL of toluene under stirring, and reacted for 1 hour.
(2) Standing for layering, separating out lower acid water, washing the upper hydrolysate to be neutral by using saturated sodium bicarbonate and distilled water to obtain hyperbranched organic silicon resin with a solvent, and removing the solvent and small molecular products of the silicon resin prepolymer at 75 ℃ by using a rotary evaporator to obtain low-viscosity solvent-free hyperbranched methyl organic silicon resin with the viscosity of: 2000 mPas, the VOC content is: 1.5 wt.% of molecular weight: 10000g/mol.
Example 8
(1) 260ML of water and 185mL of xylene were added to a three-necked flask equipped with a condenser stirrer and a thermometer, preheated at 50 ℃, 0.4mol of methyltrimethoxysilane, 0.24mol of dimethyldichlorosilane, 0.2mol of diphenyldichlorosilane and 120mL of xylene mixed solution were added through a constant pressure dropping funnel, reacted for 5 hours, and after that, 0.52mol of trimethylchlorosilane and 120mL of xylene mixed solution were added again through the constant pressure dropping funnel at 50 ℃ and stirred and mixed uniformly to react for 2 hours.
(2) Standing for layering, separating out lower acid water, washing the upper hydrolysate to be neutral by using saturated sodium bicarbonate and distilled water to obtain hyperbranched organic silicon resin with a solvent, and removing the solvent and small molecular products of the silicon resin prepolymer at 75 ℃ by using a rotary evaporator to obtain low-viscosity solvent-free hyperbranched methyl organic silicon resin with the viscosity of: 115 mPa.s, VOC content: 4.2 wt.% of molecular weight: 1800g/mol.
Example 9
(1) 280ML of water and 80mL of a methanol/80 mL of a toluene mixed solution were added to a three-necked flask equipped with a condenser stirrer and a thermometer, preheated at 65 ℃, 0.4mol of vinyltriethoxysilane, 0.36mol of diphenyldichlorosilane, 0.04mol of methylphenyldimethoxysilane and 150mL of toluene mixed solution were added through a constant pressure dropping funnel, reacted for 4 hours, then heated to 75 ℃, 0.56mol of trimethylchlorosilane and 100mL of toluene mixed solution were added through a constant pressure dropping funnel again, stirred and mixed uniformly, and reacted for 3 hours.
(2) Standing for layering, separating out lower acid water, washing the upper hydrolysate to be neutral by using saturated sodium bicarbonate and distilled water to obtain hyperbranched organic silicon resin with a solvent, and removing the solvent and small molecular products of the silicon resin prepolymer at 75 ℃ by using a rotary evaporator to obtain low-viscosity solvent-free hyperbranched methyl organic silicon resin with the viscosity of: 380 mPa.s, VOC content: 2.2 wt.% of molecular weight: 4200g/mol.
Example 10
(1) 300ML of water and 200mL of xylene were added to a three-necked flask equipped with a condenser stirrer and a thermometer, preheated at 60 ℃, 0.4mol of propyltrimethoxysilane acrylate, 0.24mol of dimethyldichlorosilane, 0.24mol of diphenyldichlorosilane, 0.12mol of methylvinyldimethoxysilane and 180mL of xylene were added through a constant pressure dropping funnel, reacted for 3 hours, then heated to 80 ℃, 0.4mol of trimethylchlorosilane and 70mL of isopropanol were added through a constant pressure dropping funnel again, stirred and mixed uniformly, and reacted for 1.5 hours.
(2) Standing for layering, separating out lower acid water, washing the upper hydrolysate to be neutral by using saturated sodium bicarbonate and distilled water to obtain hyperbranched organic silicon resin with a solvent, and removing the solvent and small molecular products of the silicon resin prepolymer at 75 ℃ by using a rotary evaporator to obtain low-viscosity solvent-free hyperbranched methyl organic silicon resin with the viscosity of: 460 mPa.s, the VOC content is: 3.8 wt.% of molecular weight: 4400g/mol.
Example 11
(1) 270ML of water and 200mL of toluene were added to a three-necked flask equipped with a condenser stirrer and a thermometer, preheated at 65℃and added with a mixture of 0.2mol of vinyltriethoxysilane, 0.2mol of propyltrimethoxysilane acrylate, 0.36mol of dimethyldichlorosilane, 0.2mol of diphenyldichlorosilane, 0.08mol of methylphenyldimethoxysilane and 160mL of toluene via a constant pressure dropping funnel, reacted for 2 hours, and then kept at 85℃and added with a mixture of 0.4mol of trimethylchlorosilane and 90mL of toluene via a constant pressure dropping funnel again, stirred and mixed uniformly, and reacted for 2 hours.
(2) Standing for layering, separating out lower acid water, washing the upper hydrolysate to be neutral by using saturated sodium bicarbonate and distilled water to obtain hyperbranched organic silicon resin with a solvent, and removing the solvent and small molecular products of the silicon resin prepolymer at 75 ℃ by using a rotary evaporator to obtain low-viscosity solvent-free hyperbranched methyl organic silicon resin with the viscosity of: 424 mPas, VOC content: 2 wt.% of molecular weight: 4100g/mol.
The viscosity of the solvent-free hyperbranched silicone resins obtained in examples 1 to 11 was measured according to the rheometer LVDV-III Ultra, the VOC content of the resin was measured according to the GB/T2793-1995 standard, and the molecular weight of the resin was measured by the gel permeation chromatograph Waters 1414.
TABLE 1 Properties of solvent-free hyperbranched Silicone resin products obtained in examples 1-11
Finally, the above embodiments are only for illustrating the technical solution of the present invention and are not limiting.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (8)
1. The synthesis method of the solvent-free hyperbranched organic silicon resin is characterized by comprising the following steps of:
Mixing an organic solvent and water, heating, slowly dropwise adding a mixed solution of a difunctional monomer A 2, a trifunctional monomer B 3 and a difunctional monomer AB 2 under the stirring condition, and then stirring and reacting for 0.5-5 hours at 50-90 ℃; then adding the monofunctional monomer C, and continuously stirring and reacting for 0.5-3 hours at 50-90 ℃; washing with water to neutrality, evaporating to remove organic solvent, and obtaining solvent-free hyperbranched organic silicon resin.
2. The method for synthesizing the solvent-free hyperbranched silicone resin according to claim 1, wherein the method comprises the following steps:
The chemical structure of the difunctional monomer A 2 is: r 2(R3)Si(R5)2; the chemical structure of trifunctional monomer B 3 is: r 1Si(R5)3; the chemical structure of the difunctional monomer AB 2 is: r 1(R2)Si(R5)2;
one of the people R1、R2、R3＝-C6H5、-(CH2)jCH3、-(CH2)kCH＝CH2、-CH2(CH2)mOCOCH＝CH2、-CH2(CH2)nOCOC(CH3)＝CH2 in the formula;
R 5 is-Cl, -O (CH 2)iCH3).
Monofunctional monomer C comprises one or more of (CH3)3SiCl、(C2H5)3SiCl、(C6H5)3SiCl、(CH3)3SiOCH3、(C2H5)3SiOC2H5、(CH3)3Si-O-Si(CH3)3、(CH3)3Si-O-Si(C2H5)3、(C2H5)3Si-O-Si(C2H5)3.
3. The method for synthesizing the solvent-free hyperbranched silicone resin according to claim 1, wherein the method comprises the following steps: the molar ratio of the difunctional monomer A 2 to the trifunctional monomer B 3 to the difunctional monomer AB 2 to the monofunctional monomer C is as follows: 1:0.7-1.5:0-0.5:0.7-1.8.
4. The method for synthesizing the solvent-free hyperbranched silicone resin according to claim 2, wherein the method comprises the following steps: in one reaction process, the hydrolysis groups of the difunctional monomer A 2 and the trifunctional monomer B 3 cannot be the same, i.e., -Cl, -OCH 3、-OC2H5 cannot be the same.
5. The method for synthesizing the solvent-free hyperbranched silicone resin according to claim 1, wherein the method comprises the following steps: the organic solvent is selected from one or more of benzene, toluene, xylene, cyclohexane, ethanol, glycol, isopropanol, n-butanol, acetone and butanone.
6. The method for synthesizing the solvent-free hyperbranched silicone resin according to claim 1, wherein the solvent addition amount is 1 to 10 times of the total mass of the reaction monomers.
7. The synthetic method of solvent-free hyperbranched silicone resin according to any one of claims 1 to 6, wherein the synthetic method is characterized by comprising the following steps:
In the middle of R1、R2、R3＝-C6H5、-(CH2)jCH3、-(CH2)kCH＝CH2、-CH2(CH2)mOCOCH＝CH2、-CH2(CH2)nOCOC(CH3)＝CH2;
Wherein R 4＝-C6H5、-(CH2)jCH3;
Wherein i, j, k, m, n are each independently selected from any integer from 0 to 5, and are not 0 at the same time.
8. The silicone resin according to claim 7, wherein the solvent-free hyperbranched silicone resin has a molecular weight of: 1800-10000g/mol, a viscosity of 80-2000 mPas at 25 ℃, a VOC content of less than 5.0wt%, more preferably less than 3.0wt%, even more preferably less than 2.0wt%.
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