CN102675572A - Application of organic silicon modifier in modified thermosetting phenolic resin - Google Patents
Application of organic silicon modifier in modified thermosetting phenolic resin Download PDFInfo
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Abstract
The invention discloses application of an organic silicon modifier in modified thermosetting phenolic resin. The organic silicon modifier is easy to prepare, and a phenolic resin system modified by the organic silicon modifier is high in uniformity and stable in quality. The thermosetting phenolic resin can be prepared from phenol, formaldehyde solution and the organic silicon modifier serving as raw materials by alkali catalytic condensation. The thermosetting phenolic resin is structurally characterized in that polydimethylsiloxane chain segments are chemically bonded to phenolic resin molecules. The prepared modified phenolic resin is difficult to moisturize; the toughness and the heat resistance of the solidified material are excellent; the toughness of a material prepared when the modified phenolic resin is applied to an impregnated material is superior to that of a common phenolic resin product; and the modified phenolic resin can be used as adhesive for preparing composite materials such as high-performance friction materials, and can effectively improve the shearing strength of an adhered position and avoid degumming.
Description
Technical field
The present invention relates to the resol field, refer more particularly to the application of a kind of organosilicon modifier in modified thermosetting phenolic resin.
Background technology
Resol is ancient kind in the macromolecular material, since 1905 its commercially produce, had century-old history so far.Owing to the resol low price, be easy to prepare, solidifies later material hardness height, Good Heat-resistance has obtained widespread use in fields such as porous plastics, coating and tackiness agent.Resol has types such as novolac resin Novolak type, heat-reactive phenolic resin Resol type, high adjacent position phenolic resin usually.Wherein heat-reactive phenolic resin Resol type is an important kind of resol; This resin has characteristics such as reactive behavior is big, solid content height, especially is fit to high performance materials such as preparation phenolic foamed plastics, polyurethane material, phenolic composite, foundry resin.But heat-reactive phenolic resin also has many defectives when possessing above advantage, higher like the viscosity of resin, and the storage time of resin is limited, solidify later material and be prone to embrittlement, and poor toughness, easy suction is made moist, and resistance toheat is limited etc.
To after the heat-reactive phenolic resin modification, can improve each item performance of thermosetting resin through organosilicon, discloseder organic-silicon-modified heat-reactive phenolic resins of past mainly are divided into two big types; One type is to realize the modification purpose through physical blending; The resin system consistency of this method preparation is poor, influences the goods mechanical property, and also having one big type is that organoalkoxysilane is added phenolic system; Pass through tetraethoxysilane and resol blend are improved its film-forming properties like Japanese Patent JP7268276A; But the resin structure that this technology makes is difficult to regulation and control, MWD broad, unstable product quality.
Publication number is that the Chinese patent of CN 101724226 B has used a kind of hyper-branched silicone resin that contains active function groups that thermosetting resin has been carried out modification, has improved performances such as toughness and thermostability.Publication number is that the Chinese patent of CN 10197420 B has used a kind of organic sericite that heat-reactive phenolic resin has been carried out modification; Improved the thermotolerance of resol; But this technology also is difficult to the degree of organic sericite and phenolic aldehyde molecular reaction is carried out meticulous control; The resin structure and the MWD that make are uncertain, unstable product quality.
Summary of the invention
The invention discloses the application of a kind of organosilicon modifier in modified thermosetting phenolic resin; Resin structure MWD by this organosilicon modifier makes is confirmed; Constant product quality improves a lot with matrix material thermotolerance, mechanical property and the insulating property of its preparation.
The application of a kind of organosilicon modifier in modified thermosetting phenolic resin, the general structure of described organosilicon modifier is following:
In the formula I, n is 1 ~ 500 integer, R
1Be hydroxyl, alkoxyl group, allyl group ether or glycidyl ether, R
2, R
3Be positioned at R
1Ortho position or contraposition, be hydrogen, alkyl or alkoxyl group.Wherein, R
1Ortho position and para-orienting group in have at least one to be hydrogen.
Silicone resin has the Si-O bond structure of similar inorganic silicate in forming the cubic network structure, the bond energy of Si-O key is more much bigger than the bond energy of C-C key, and therefore destroying the Si-O key just needs more energy, the i.e. higher temperature of silicone resin ability.The material of therefore organic-silicon-modified heat-reactive phenolic resin preparation generally has the thermotolerance height, thermal weight loss is little and the toughness advantages of higher.
Traditional modifying agent is that the resol for preparing is carried out modification as silicate class materials such as tetraethoxy, and therefore the degree to modification is difficult to meticulous control, and the resin structure and the MWD that make are uncertain, unstable product quality.Organosilicon modifier provided by the invention; Has particular structural; Can participate in the middle of the step of condensation that generates resol; Can carry out meticulous control to the degree of modification, chemically bonded YSR 3286 segment in the resol molecule more efficiently, and also the quality product that obtains is more stable.
The scope of the n value of the organosilicon modifier among the present invention is adjustable; The increase of n value can improve the toughness and the thermotolerance of the prepared material of this resinoid; But the n value increases the rising that also can cause cost; Take all factors into consideration various factors, the span of n value is preferably 1 ~ 50 integer, more preferably 1 ~ 5 integer.
The preparation method of the organosilicon modifier described in the present invention is following:
Under catalyst action, compound (II) and compound (III) are mixed reacting generating compound (I).
This reaction is represented as follows with chemical equation:
Among formula (II), (III), (V), R
1Be hydroxyl, alkoxyl group, allyl group ether or glycidyl ether, R
2, R
3Be positioned at R
1Ortho position or contraposition, be hydrogen, alkyl or alkoxyl group, allyl group is positioned at R in the formula (II)
1Ortho position or contraposition, n is 1 ~ 500 integer.Wherein, R
1Ortho position and para-orienting group at least one is a hydrogen.
Described preparation method specifically can be:
With compound (II) and catalyst mix; Stirring is warming up to 55 ~ 65 ℃; Compound (III) is added dropwise in the mixture, and keeps temperature of reaction not to be higher than 80 ℃, compound (II): compound (III) mol ratio is 1.5-3: 1; Reaction proceeds to and after the phenomenon that heats up stops, continues end in 2 ~ 3 hours again, and productive rate is greater than 90%.
As described R
2Be hydrogen, R
3Be methyl or methoxy, raw material is easy to get, and the organosilicon modifier cost of preparation is low, is fit to large-scale application.Therefore described compound (II) can be preferably Eugenol, methyl eugenol, o-allyl phenol and p-allylphenol and their ether compound.
Described catalyzer is the compound that contains Pt, and this compound that contains Pt comprises Pt metallic complex salt or Pt metal acid, is preferably the solution of Platinic chloride or Platinic chloride, and solvent is preferably Virahol, toluene or THF in the solution of said Platinic chloride.
Described catalyst consumption is in Pt, and the massfraction of Pt in whole reaction system is 1.0 * 10
-5～6.0 * 10
-5, in this reaction, catalyst consumption is few, and catalyzer has higher TON value, and this has effectively reduced the cost of this method.
The method of above-mentioned organosilicon modifier modified thermosetting phenolic resin, specifically can for:
Phenol and said organosilicon modifier are mixed, under alkaline condition, stir and be warming up to 55 ~ 60 ℃; Splash into formaldehyde solution then, dropwise back insulation 10 ~ 60min, be warming up to 80 ~ 95 ℃ of reaction 100 ~ 150min again; Add acid and be neutralized to pH=7, under heated condition, the decompression vacuum pumping dehydration is 60 ~ 80 ℃ until temperature; It is even to add stirring solvent, promptly makes heat-reactive phenolic resin.
Through changing the ratio of raw material, the ratio that can regulate Si-O key in the system that obtains, and then each item performance of regulating novolac resin.The weight ratio of described phenol and organosilicon modifier is 1.6～16: 1; The massfraction of formaldehyde solution is 30 ~ 50%, is preferably 37%, and the mass ratio of formaldehyde solution and phenol is 0.8～5.0: 1, and described solvent can be selected ethanol for use.Alkaline condition generally adds sodium hydroxide and realizes that sodium hydroxide: phenol is preferably 2～6: 100 in system.
The invention also discloses a kind of organic-silicon-modified heat-reactive phenolic resin that utilizes said organosilicon modifier preparation, under alkaline condition, it is made by described organosilicon modifier, phenol and formolite reaction.
The general formula of described organic-silicon-modified heat-reactive phenolic resin primary structure is following:
Wherein, n is 1 ~ 500 integer, R
1Be hydroxyl, alkoxyl group or glycidyl ether, R
2, R
3Be positioned at R
1Ortho position or contraposition, be hydrogen, alkyl or alkoxyl group, Resol1, Resol2 are positioned at R
1Ortho position or contraposition, expression heat-reactive phenolic resin segmented structure.
Compare with prior art, beneficial effect of the present invention is embodied in:
(1) organosilicon modifier provided by the invention realizes that through chemical reaction the phenolic resin system homogeneity that makes is good, constant product quality to STUDY ON THE MODIFICATION OF PENOLIC RESIN;
(2) activity of organosilicon modifier can be regulated through changing substituting group, and then can regulate the performance of the resol that obtains;
(3) organosilicon modifier preparation of the present invention is easy, and raw material is easy to get, and is fit to large-scale application;
(4) Recipe of the present invention makes when effectively controlling cost that building-up process is easy to save time, and the resol storage time of processing is longer, is difficult for suction, and physico-chemical property is stable, toughness and Good Heat-resistance after the material cured.
Description of drawings
Fig. 1 is embodiment 1 an Eugenol type organosilicon modifier nuclear magnetic spectrogram;
Fig. 2 is embodiment 3 allyl phenol type organosilicon modifier nuclear magnetic spectrograms;
Fig. 3 is each embodiment resol performance test results chart.
Embodiment
Embodiment 1
With Eugenol (164kg, 1000mol) and isopropyl alcohol solution of chloroplatinic acid (platinum quality percentage composition 0.8%) 14.76g add synthesis reaction vessel, stir and to be warming up to about 60 ℃; With 1,1,3; The 3-tetramethyl disiloxane (67kg, 500mol) dropping advances to keep in the reaction kettle temperature not to be higher than 80 ℃ in batches, and reaction proceeds to and after the phenomenon that heats up stops, finished promptly to make organosilicon modifier again in lasting 2 ~ 3 hours; Productive rate 93%, the structural formula and the nuclear magnetic spectrogram of this organosilicon modifier are as shown in Figure 1.
Phenol 80kg, organosilicon modifier 10kg, sodium hydroxide 2.7kg are added synthesis reaction vessel, heat up and stir, temperature rises to about 60 ℃; Drip massfraction 37% formaldehyde solution 100kg, drip to finish and be warming up to 80 ~ 85 ℃ of reaction 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%; Decompression vacuum pumping dehydration under heated condition; Be about 70 ℃ until temperature, stop heating, add 20kg ethanol and stir to such an extent that brown is clarified resin solution.The organic silicon modified phenolic resin of this method preparation is suitable as tackiness agent.
Nuclear magnetic data:
1H?NMR(500MHz,DMSO-d6,TMS):δ=0.4(12H,Si-CH
3),1.5(4H,Si-CH
2-),1.8(4H,Si-C-CH
2-),2.6(4H,Si-C-C-CH
2-),3.5(12H,Ar-O-CH
3)3.6-3.8(90H,Ar-CH
2-Ar),4.55-4.80(24H,Ar-CH
2-O-CH
2-Ar),6.80-7.21(112H,Ar-H)。
With Eugenol (82kg, 500mol) and isopropyl alcohol solution of chloroplatinic acid (platinum quality percentage composition 0.8%) 8.77g add synthesis reaction vessel, stir and to be warming up to about 60 ℃; With 1,1,3; 3-tetramethyl disiloxane (33.5kg; 250mol) dropping advances to keep in the reaction kettle temperature not to be higher than 80 ℃ in batches, and reaction proceeds to and after the phenomenon that heats up stops, finished promptly to process organosilicon modifier, productive rate 94% again in lasting 2 ~ 3 hours.
With phenol 100kg, organosilicon modifier 10kg, sodium hydroxide 3.3kg and adding synthesis reaction vessel, heat up and stir, temperature rises to about 60 ℃; Drip formaldehyde solution 285kg (37wt%), drip to finish and be warming up to 80 ~ 85 ℃ of reaction 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%; Decompression vacuum pumping dehydration under heated condition; Be about 90 ℃ until temperature, stop heating, add 40kg ethanol and stir to such an extent that brown is clarified resin solution.The organic silicon modified phenolic resin of this method preparation is suitable as impregnant.
Nuclear magnetic data:
1H?NMR(500MHz,DMSO-d6,TMS):δ=0.4(12H,Si-CH
3),1.5(4H,Si-CH
2-),1.8(4H,Si-C-CH
2-),2.6(4H,Si-C-C-CH
2-),3.5(6H,Ar-O-CH
3)3.6-3.8(102H,Ar-CH
2-Ar),4.55-4.80(28H,Ar-CH
2-O-CH
2-Ar),6.80-7.21(102H,Ar-H)
With the 2-allyl phenol (133kg, 1000mol) and isopropyl alcohol solution of chloroplatinic acid (platinum quality percentage composition 0.8%) 14.76g add synthesis reaction vessel, stir and to be warming up to about 60 ℃; With 1; 1,3,3-tetramethyl disiloxane (67kg; 500mol) dropping advances to keep in the reaction kettle temperature not to be higher than 80 ℃ in batches; Reaction proceeds to and after the phenomenon that heats up stops, finished in lasting 2 ~ 3 hours more promptly to process 2-allyl phenol type organosilicon modifier, productive rate 91%, and the structural formula and the nuclear magnetic spectrogram of this allyl phenol type organosilicon modifier are as shown in Figure 2.
Phenol 80kg, organosilicon modifier 10kg and sodium hydroxide 2.7kg are added synthesis reaction vessel, heat up and stir, temperature rises to about 60 ℃; Drip quality percentage composition 37% formaldehyde solution 100kg, drip Bi Baowen for some time, and then be warming up to 90 ~ 95 ℃ of reaction 130min; Hydrochloric acid with massfraction 5% is neutralized to pH=7, and the decompression vacuum pumping dehydration is about 70 ℃ until temperature under heated condition; Stop heating, add 20kg ethanol and stir to such an extent that brown is clarified resin solution.
Nuclear magnetic data:
1H?NMR(500MHz,DMSO-d6,TMS):δ=0.4(12H,Si-CH
3),1.5(4H,Si-CH
2-),1.8(4H,Si-C-CH
2-),2.6(4H,Si-C-C-CH
2-),3.6-3.8(108H,Ar-CH
2-Ar),4.55-4.80(14H,Ar-CH
2-O-CH
2-Ar),6.80-7.21(105H,Ar-H)
With the 2-allyl phenol (66.5kg, 500mol) and isopropyl alcohol solution of chloroplatinic acid (platinum quality percentage composition 0.8%) 8.77g add synthesis reaction vessel, stir and to be warming up to about 60 ℃; With 1,1,3; 3-tetramethyl disiloxane (33.5kg; 250mol) dropping advances to keep in the reaction kettle temperature not to be higher than 80 ℃ in batches, and reaction proceeds to and after the phenomenon that heats up stops, finished promptly to process organosilicon modifier, productive rate 92% again in lasting 2 ~ 3 hours.
Phenol 100kg, organosilicon modifier 10kg and sodium hydroxide 3.3kg are added synthesis reaction vessel, heat up and stir, temperature rises to about 60 ℃; Drip quality percentage composition 37% formaldehyde solution 285kg, drip to finish and be warming up to 90 ~ 95 ℃, react 130min with this understanding; Hydrochloric acid with massfraction 5% is neutralized to pH=7, and the decompression vacuum pumping dehydration is about 90 ℃ until temperature under heated condition; Stop heating, add 40kg ethanol and stir to such an extent that brown is clarified resin solution.
Nuclear magnetic data:
1H?NMR(500MHz,DMSO-d6,TMS):δ=0.4(12H,Si-CH
3),1.5(4H,Si-CH
2-),1.8(4H,Si-C-CH
2-),2.6(4H,Si-C-C-CH
2-),3.6-3.8(120H,Ar-CH
2-Ar),4.55-4.80(20H,Ar-CH
2-O-CH
2-Ar),6.80-7.21(112H,Ar-H)。
(82kg 500mol) adds synthesis reaction vessel with Platinic chloride 9g, stirs to be warming up to about 60 ℃, with 1 with Eugenol; 1,3,3,5; 5,7,7-prestox tetrasiloxane (99.7kg; 352mol) dropping advances to keep in the reaction kettle temperature not to be higher than 80 ℃ in batches, and reaction proceeds to and after the phenomenon that heats up stops, finished promptly to process organosilicon modifier, productive rate 95% again in lasting 2 ~ 3 hours.
Phenol 100kg, organosilicon modifier 10kg and sodium hydroxide 3.3kg are added synthesis reaction vessel, heat up and stir, temperature rises to about 60 ℃; Drip quality percentage composition 37% formaldehyde solution 285kg, drip to finish and be warming up to 90 ~ 95 ℃, react 130min with this understanding; Hydrochloric acid with massfraction 5% is neutralized to pH=7, and the decompression vacuum pumping dehydration is about 90 ℃ until temperature under heated condition; Stop heating, add 40kg ethanol and stir to such an extent that brown is clarified resin solution.
Nuclear magnetic data:
1H?NMR(500MHz,DMSO-d6,TMS):δ=0.4(12H,Si-CH
3),1.5(4H,Si-CH
2-),1.8(4H,Si-C-CH
2-),2.6(4H,Si-C-C-CH
2-),3.5(6H,Ar-O-CH
3)3.6-3.8(110H,Ar-CH
2-Ar),4.55-4.80(18H,Ar-CH
2-O-CH
2-Ar),6.80-7.21(95H,Ar-H)。
Embodiment 6
With Eugenol (82kg; 500mol) add synthesis reaction vessel with Platinic chloride 9g; Stirring is warming up to about 60 ℃, and (256.6kg 352mol) drips to keep in the reaction kettle temperature not to be higher than 80 ℃ in batches with two decamethyls, ten siloxanes; Reaction proceeds to and after the phenomenon that heats up stops, finished promptly to process organosilicon modifier, productive rate 94% again in lasting 2 ~ 3 hours.
Phenol 100kg, organosilicon modifier 10kg and sodium hydroxide 3.3kg are added synthesis reaction vessel, heat up and stir, temperature rises to about 60 ℃; Drip quality percentage composition 37% formaldehyde solution 285kg, drip to finish and be warming up to 90 ~ 95 ℃, react 130min with this understanding; Hydrochloric acid with massfraction 5% is neutralized to pH=7, and the decompression vacuum pumping dehydration is about 90 ℃ until temperature under heated condition; Stop heating, add 40kg ethanol and stir to such an extent that brown is clarified resin solution.
Nuclear magnetic data:
1H?NMR(500MHz,DMSO-d6,TMS):δ=0.4(12H,Si-CH
3),1.5(4H,Si-CH
2-),1.8(4H,Si-C-CH
2-),2.6(4H,Si-C-C-CH
2-),3.5(6H,Ar-O-CH
3)3.6-3.8(94H,Ar-CH
2-Ar),4.55-4.80(16H,Ar-CH
2-O-CH
2-Ar),6.80-7.21(95H,Ar-H)。
Embodiment 7
With methyl eugenol (178kg, 1000mol) and isopropyl alcohol solution of chloroplatinic acid (platinum quality percentage composition 0.8%) 14.76g add synthesis reaction vessel, stir and to be warming up to about 60 ℃; With 1,1,3; 3-tetramethyl disiloxane (67kg; 500mol) dropping advances to keep in the reaction kettle temperature not to be higher than 80 ℃ in batches, and reaction proceeds to and after the phenomenon that heats up stops, finished promptly to process organosilicon modifier, productive rate 91% again in lasting 2 ~ 3 hours.
Phenol 80kg, organosilicon modifier 10kg, sodium hydroxide 2.7kg are added synthesis reaction vessel, heat up and stir, temperature rises to about 60 ℃; Drip massfraction 37% formaldehyde solution 100kg, drip to finish and be warming up to 80 ~ 85 ℃ of reaction 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%; Decompression vacuum pumping dehydration under heated condition; Be about 70 ℃ until temperature, stop heating, add 20kg ethanol and stir to such an extent that brown is clarified resin solution.The organic silicon modified phenolic resin of this method preparation is suitable as tackiness agent.
Nuclear magnetic data:
1H?NMR(500MHz,DMSO-d6,TMS):δ=0.4(12H,Si-CH
3),1.5(4H,Si-CH
2-),1.8(4H,Si-C-CH
2-),2.6(4H,Si-C-C-CH
2-),3.5(12H,Ar-O-CH
3)3.6-3.8(102H,Ar-CH
2-Ar),4.55-4.80(22H,Ar-CH
2-O-CH
2-Ar),6.80-7.21(112H,Ar-H)。
With methyl eugenol (89kg; 500mol) add synthesis reaction vessel with Platinic chloride 9g; Stirring is warming up to about 60 ℃, and (256.6kg 352mol) drips to keep in the reaction kettle temperature not to be higher than 80 ℃ in batches with two decamethyls, ten siloxanes; Reaction proceeds to and after the phenomenon that heats up stops, finished promptly to process organosilicon modifier, productive rate 95% again in lasting 2 ~ 3 hours.
Phenol 100kg, organosilicon modifier 10kg and sodium hydroxide 3.3kg are added synthesis reaction vessel, heat up and stir, temperature rises to about 60 ℃; Drip quality percentage composition 37% formaldehyde solution 285kg, drip to finish and be warming up to 90 ~ 95 ℃, react 130min with this understanding; Hydrochloric acid with massfraction 5% is neutralized to pH=7, and the decompression vacuum pumping dehydration is about 90 ℃ until temperature under heated condition; Stop heating, add 40kg ethanol and stir to such an extent that brown is clarified resin solution.
Nuclear magnetic data:
1H?NMR(500MHz,DMSO-d6,TMS):δ=0.4(12H,Si-CH
3),1.5(4H,Si-CH
2-),1.8(4H,Si-C-CH
2-),2.6(4H,Si-C-C-CH
2-),3.5(12H,Ar-O-CH
3)3.6-3.8(102H,Ar-CH
2-Ar),4.55-4.80(18H,Ar-CH
2-O-CH
2-Ar),6.80-7.21(112H,Ar-H)。
The structural formula of the heat-reactive phenolic resin that the nuclear magnetic data explanation of embodiment 1 ~ 8 makes meets the structure shown in the formula IV.
Reference example 1
Phenol 90kg and sodium hydroxide 2.7kg are added synthesis reaction vessel, heat up and stir, temperature rises to about 60 ℃; Drip quality percentage composition 37% formaldehyde solution 100kg, and then be warming up to 90 ~ 95 ℃ of reaction 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%; Decompression vacuum pumping dehydration under heated condition; Be about 70 ℃ until temperature, stop heating, add 20kg ethanol stir brown clarified liq resin solution.
Reference example 2
Phenol 110kg and sodium hydroxide 3.3kg are added synthesis reaction vessel, heat up and stir, temperature rises to about 60 ℃; Drip quality percentage composition 37% formaldehyde solution 285kg, and then be warming up to 90 ~ 95 ℃ of reaction 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%; Decompression vacuum pumping dehydration under heated condition; Be about 90 ℃ until temperature, stop heating, add 40kg ethanol and stir to such an extent that brown is clarified resin solution.
The resol property comparison that Fig. 3 prepares for heat-reactive phenolic resin and usual way through this modifying agent preparation; Can know according to Fig. 3; The introducing of organosilicon modifier can effectively reduce the free phenol content of resin, and the unmodified resin of viscosity ratio is low, and its degradation temperature significantly promotes.Comprehensive above data can know that organosilicon modifier can effectively improve each item performance index of Resol type resin.
Performance characterization method:
1. viscosity measurement is abideed by the liquid and solution shape resol viscosimetric analysis of HG/T 2712-95 China chemical industry standard, measures 25 ℃ of temperature.
2. solid content is abideed by GB GB-T2793-1995 mensuration.
3. free phenol content is used iodometric determination in accordance with GB GB-T 7130-1986.
4. degradation temperature is resin to be got the 6-10mg sample under nitrogen atmosphere, heat with the temperature rise rate of thermogravimetric analyzer with 10 ℃/min behind 150 ℃ of abundant down curing, in weightless 5% o'clock temperature.
Claims (10)
1. the application of organosilicon modifier in modified thermosetting phenolic resin is characterized in that the general structure of described organosilicon modifier is following:
In the formula I, n is 1 ~ 500 integer, R
1Be hydroxyl, alkoxyl group, allyl group ether or glycidyl ether, R
2, R
3Be positioned at R
1Ortho position or contraposition, be hydrogen, alkyl or alkoxyl group.
2. application according to claim 1 is characterized in that, described n is 1 ~ 50 integer.
3. application according to claim 1 is characterized in that, described R
2Be hydrogen, R
3Be methyl or methoxy.
4. application according to claim 3 is characterized in that, described n=1 or 9, R
1Be methoxyl group, R
3Be positioned at R
1The ortho position.
5. application according to claim 3 is characterized in that, described n=1,3 or 9, R
1Be hydroxyl, R
3Be positioned at R
1The ortho position.
6. application according to claim 1 is characterized in that, described n=1, R
1Be hydroxyl, R
3Be hydrogen.
7. according to the arbitrary described application of claim 1 ~ 6, it is characterized in that, comprising: phenol and said organosilicon modifier are mixed, under alkaline condition; Stirring is warming up to 55 ~ 60 ℃, splashes into formaldehyde solution then, dropwises back insulation 10 ~ 60min; Be warming up to 80 ~ 95 ℃ of reaction 100 ~ 150min again, add acid and be neutralized to pH=7, under heated condition; The decompression vacuum pumping dehydration is 60 ~ 80 ℃ until temperature, and the adding stirring solvent is even, promptly makes organic-silicon-modified heat-reactive phenolic resin.
8. application according to claim 7 is characterized in that, the weight ratio of described phenol and organosilicon modifier is 1.6～16: 1; The massfraction of formaldehyde solution is 30 ~ 50%, and the mass ratio of formaldehyde solution and phenol is 0.8～5.0: 1.
9. organic-silicon-modified heat-reactive phenolic resin is characterized in that general structure is shown in formula IV:
Wherein, n is 1 ~ 500 integer, R
1Be hydroxyl, alkoxyl group, allyl group ether or glycidyl ether, R
2, R
3Be positioned at R
1Ortho position or contraposition, be hydrogen, alkyl or alkoxyl group, Resol1, Resol2 are positioned at R
1Ortho position or contraposition, expression heat-reactive phenolic resin segmented structure.
10. organic-silicon-modified heat-reactive phenolic resin according to claim 9 is characterized in that, described R
1Be hydroxyl or alkoxyl group.
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| CN105131877A (en) * | 2015-08-24 | 2015-12-09 | 江西省科学院应用化学研究所 | Silane modified phenolic resin adhesive |
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| CN105754062A (en) * | 2016-03-15 | 2016-07-13 | 东北林业大学 | Low-hydroscopicity phenolic resin insulating gel and preparation method thereof |
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| CN106496473B (en) * | 2016-09-20 | 2018-09-04 | 中国科学院化学研究所 | A kind of Effect of Organosilicon-modified Phenol-formaldehyde Resin and preparation method thereof |
| CN106565923A (en) * | 2016-11-02 | 2017-04-19 | 中国林业科学研究院林产化学工业研究所 | Silicon-containing epoxy anacardol-group phenolic resin, and preparation method and application of silicon-containing epoxy anacardol-group phenolic resin |
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| CN110591029B (en) * | 2019-09-30 | 2021-10-26 | 河南工业大学 | Preparation method for synthesizing organic silicon modified phenolic resin by ester exchange method |
| CN110698619A (en) * | 2019-11-26 | 2020-01-17 | 南通百川新材料有限公司 | Modified phenolic resin and preparation method thereof |
| CN112851903A (en) * | 2021-01-12 | 2021-05-28 | 浙江多邦新材料有限公司 | Preparation method of organic silicon modified waterborne polyurethane and product thereof |
| CN114196024A (en) * | 2022-01-10 | 2022-03-18 | 万华化学集团股份有限公司 | Organic silicon modified phenolic resin and preparation method and application thereof |
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