CN102675572B - Application of organic silicon modifier in modified thermosetting phenolic resin - Google Patents
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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 resol field, refer more particularly to the application of a kind of organosilicon modifier in modified thermosetting phenolic resin.
Background technology
Resol is an ancient kind in macromolecular material, since 1905 its commercially produce, had so far century-old history.Due to resol low price, be easy to preparation, to solidify later material hardness high, Good Heat-resistance, is widely applied in fields such as porous plastics, coating and tackiness agent.Resol has the types such as novolac resin Novolak type, heat-reactive phenolic resin Resol type, high adjacent position phenolic resin conventionally.Wherein heat-reactive phenolic resin Resol type is an important kind of resol, this resin has that reactive behavior is large, solid content high, is especially applicable to preparing phenolic foamed plastics, polyurethane material, phenolic composite, the contour performance materials of foundry resin.But heat-reactive phenolic resin also has many defects in possessing above advantage, as higher in the viscosity of resin, and the storage time of resin is limited, solidify the later easy embrittlement of material, poor toughness, easily water suction is made moist, and resistance toheat is limited etc.
By organosilicon to after heat-reactive phenolic resin modification, can improve the properties of thermosetting resin, discloseder organic-silicon-modified heat-reactive phenolic resins of past are mainly divided into two large classes, one class is to realize modification object by physical blending, resin system consistency prepared by the method is poor, affect Mechanical Properties of Products, also having a large class is that organoalkoxysilane is added to phenolic system, if Japanese Patent JP7268276A is by improving its film-forming properties by tetraethoxysilane and resol blend, but the resin structure that this technique makes is difficult to regulation and control, molecular weight distribution is wider, 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 to carry out modification to thermosetting resin, has improved the performance such as toughness and thermostability.Publication number is that the Chinese patent of CN 10197420 B has used a kind of organic sericite to carry out modification to heat-reactive phenolic resin, improve the thermotolerance of resol, but this technique is also difficult to the degree of organic sericite and phenolic aldehyde molecular reaction to carry out meticulous control, the resin structure and the molecular weight distribution 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, the resin structure molecular weight distribution being made by this organosilicon modifier is determined, constant product quality, matrix material thermotolerance, mechanical property and the insulating property prepared with it improve a lot.
The application of organosilicon modifier in modified thermosetting phenolic resin, the general structure of described organosilicon modifier is as follows:
In formula I, the integer that n is 1 ~ 500, R
1for 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 one at least for hydrogen.
Silicone resin has the Si-O bond structure of similar inorganic silicate in formation dimensional network structure, and the bond energy of Si-O key is more much bigger than the bond energy of C-C key, and therefore destroying Si-O key just needs more energy, the i.e. higher temperature of silicone resin ability.Therefore the material that prepared by organic-silicon-modified heat-reactive phenolic resin generally has that thermotolerance is high, thermal weight loss is little and toughness advantages of higher.
Traditional modifying agent is that the resol to preparing carries out modification as the silicate class materials such as tetraethoxy, therefore the degree of modification is difficult to meticulous control, and the resin structure and the molecular weight distribution that make are uncertain, unstable product quality.Organosilicon modifier provided by the invention, there is special structure, can participate in the middle of the step of condensation that generates resol, can carry out meticulous control to the degree of modification, chemical bonding PolydimethylsiloxaneChain Chain section in resol molecule more efficiently, and the quality product obtaining is more stable.
The scope of the n value of the organosilicon modifier in the present invention is adjustable, the increase of n value can improve toughness and the thermotolerance of the prepared material of this resinoid, but n value increases the rising that also can cause cost, consider 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 as follows:
Under catalyst action, compound (II) and compound (III) are mixed to reacting generating compound (I).
This reaction is expressed as follows with chemical equation:
In formula (II), (III), (V), R
1for 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 formula (II)
1ortho position or contraposition, the integer that n is 1 ~ 500.Wherein, R
1ortho position and para-orienting group at least one is hydrogen.
Described preparation method can be specifically:
By compound (II) and catalyst mix, stirring is warming up to 55 ~ 65 DEG C, compound (III) is added dropwise in mixture, and keep temperature of reaction not higher than 80 DEG C, compound (II): compound (III) mol ratio is 1.5-3: 1, reaction proceeds to and after intensification phenomenon stops, continues to finish for 2 ~ 3 hours again, and productive rate is greater than 90%.
As described R
2for hydrogen, R
3for methyl or methoxy, raw material is easy to get, and the organosilicon modifier cost of preparation is low, is applicable 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 containing Pt, should comprise Pt metallic complex salt or Pt metal acid containing the compound of Pt, is preferably the solution of Platinic chloride or Platinic chloride, and in the solution of described Platinic chloride, solvent is preferably Virahol, toluene or tetrahydrofuran (THF).
The consumption of described catalyzer is in Pt, and the massfraction of Pt in whole reaction system is 1.0 × 10
-5～6.0 × 10
-5, in this reaction, the consumption of catalyzer is few, and catalyzer has higher TON value, and this effectively reduces the cost of the method.
The method of above-mentioned organosilicon modifier modified thermosetting phenolic resin, is specifically as follows:
Phenol and described organosilicon modifier are mixed, under alkaline condition, stirring is warming up to 55 ~ 60 DEG C, then splashes into formaldehyde solution, dropwises rear insulation 10 ~ 60min, be warming up to again 80 ~ 95 DEG C of reaction 100 ~ 150min, add acid to be neutralized to pH=7, under heated condition, decompression vacuum pumping dewaters until temperature is 60 ~ 80 DEG C, add stirring solvent even, make heat-reactive phenolic resin.
By the ratio of feed change, can regulate the ratio of Si-O key in the system obtaining, and then regulate the properties of novolac resin.Described phenol and the weight ratio of organosilicon modifier are 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.Alkaline condition generally adds sodium hydroxide to realize in system, sodium hydroxide: phenol is preferably 2～6: 100.
The invention also discloses the organic-silicon-modified heat-reactive phenolic resin of the one of utilizing described organosilicon modifier to prepare, under alkaline condition, it is made by described organosilicon modifier, phenol and formaldehyde reaction.
The general formula of described organic-silicon-modified heat-reactive phenolic resin primary structure is as follows:
Wherein, the integer that n is 1 ~ 500, R
1for 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, represent heat-reactive phenolic resin segmented structure.
Compared with the existing technology, beneficial effect of the present invention is embodied in:
(1) organosilicon modifier provided by the invention is realized by chemical reaction the modification of resol, and the phenolic resin system homogeneity making is good, constant product quality;
(2) activity of organosilicon modifier can regulate by changing substituting group, and then can regulate the performance of the resol obtaining;
(3) easily, raw material is easy to get, and is applicable to large-scale application in organosilicon modifier preparation of the present invention;
(4) Recipe of the present invention makes in effectively controlling cost that building-up process is easy to save time, and the resol storage time of making is longer, is difficult for water suction, and physico-chemical property is stable, toughness and Good Heat-resistance after material cured.
Brief description of the drawings
Fig. 1 is embodiment 1 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
By Eugenol (164kg, 1000mol) and isopropyl alcohol solution of chloroplatinic acid (platinum quality percentage composition 0.8%) 14.76g add synthesis reaction vessel, stirring is warming up to 60 DEG C of left and right, by 1,1,3,3-tetramethyl disiloxane (67kg, 500mol) drips in batches in reactor and keeps temperature not higher than 80 DEG C, and reaction proceeds to and after intensification phenomenon stops, continues to finish to make for 2 ~ 3 hours organosilicon modifier again, productive rate 93%, the structural formula of this organosilicon modifier and nuclear magnetic spectrogram are as shown in Figure 1.
Phenol 80kg, organosilicon modifier 10kg, sodium hydroxide 2.7kg are added to synthesis reaction vessel, heat up and stir, temperature rises to approximately 60 DEG C, drip massfraction 37% formaldehyde solution 100kg, drip to finish and be warming up to 80 ~ 85 DEG C of reaction 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%, decompression vacuum pumping dehydration under heated condition, until temperature is about 70 DEG C, stop heating, add 20kg ethanol to stir and to obtain brown clarification resin solution.The standby Effect of Organosilicon-modified Phenol-formaldehyde Resin of this legal system 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)。
Embodiment 2
By Eugenol (82kg, 500mol) and isopropyl alcohol solution of chloroplatinic acid (platinum quality percentage composition 0.8%) 8.77g add synthesis reaction vessel, stirring is warming up to 60 DEG C of left and right, by 1,1,3,3-tetramethyl disiloxane (33.5kg, 250mol) drip in batches in reactor and keep temperature not higher than 80 DEG C, reaction proceeds to and after intensification phenomenon stops, continues to finish to make for 2 ~ 3 hours organosilicon modifier, productive rate 94% again.
By phenol 100kg, organosilicon modifier 10kg, sodium hydroxide 3.3kg with add synthesis reaction vessel, heat up and stir, temperature rises to approximately 60 DEG C, drip formaldehyde solution 285kg(37wt%), drip to finish and be warming up to 80 ~ 85 DEG C of reaction 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%, decompression vacuum pumping dehydration under heated condition, until temperature is about 90 DEG C, stop heating, add 40kg ethanol to stir and to obtain brown clarification resin solution.The standby Effect of Organosilicon-modified Phenol-formaldehyde Resin of this legal system 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)
Embodiment 3
By 2-allyl phenol (133kg, 1000mol) and isopropyl alcohol solution of chloroplatinic acid (platinum quality percentage composition 0.8%) 14.76g add synthesis reaction vessel, stirring is warming up to 60 DEG C of left and right, by 1,1,3,3-tetramethyl disiloxane (67kg, 500mol) drip in batches in reactor and keep temperature not higher than 80 DEG C, reaction proceeds to and after intensification phenomenon stops, continues to finish to make for 2 ~ 3 hours 2-allyl phenol type organosilicon modifier again, productive rate 91%, the structural formula of this allyl phenol type organosilicon modifier and nuclear magnetic spectrogram are as shown in Figure 2.
Phenol 80kg, organosilicon modifier 10kg and sodium hydroxide 2.7kg are added to synthesis reaction vessel, heat up and stir, temperature rises to approximately 60 DEG C, drips quality percentage composition 37% formaldehyde solution 100kg, drips Bi Baowen for some time, and then be warming up to 90 ~ 95 DEG C reaction 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%, decompression vacuum pumping dehydration under heated condition, until temperature is about 70 DEG C, stop heating, add 20kg ethanol to stir and to obtain brown clarification 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)
Embodiment 4
By 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, stirring is warming up to 60 DEG C of left and right, by 1,1,3,3-tetramethyl disiloxane (33.5kg, 250mol) drip in batches in reactor and keep temperature not higher than 80 DEG C, reaction proceeds to and after intensification phenomenon stops, continues to finish to make for 2 ~ 3 hours organosilicon modifier, productive rate 92% again.
Phenol 100kg, organosilicon modifier 10kg and sodium hydroxide 3.3kg are added to synthesis reaction vessel, heat up and stir, temperature rises to approximately 60 DEG C, drips quality percentage composition 37% formaldehyde solution 285kg, drips to finish to be warming up to 90 ~ 95 DEG C, react with this understanding 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%, decompression vacuum pumping dehydration under heated condition, until temperature is about 90 DEG C, stop heating, add 40kg ethanol to stir and to obtain brown clarification 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)。
Embodiment 5
Eugenol (82kg, 500mol) and Platinic chloride 9g are added to synthesis reaction vessel, stir and be warming up to 60 DEG C of left and right, by 1,1,3,3,5,5,7,7-octamethylcyclotetrasiloxane (99.7kg, 352mol) drip in batches in reactor and keep temperature not higher than 80 DEG C, reaction proceeds to and after intensification phenomenon stops, continues to finish to make for 2 ~ 3 hours organosilicon modifier, productive rate 95% again.
Phenol 100kg, organosilicon modifier 10kg and sodium hydroxide 3.3kg are added to synthesis reaction vessel, heat up and stir, temperature rises to approximately 60 DEG C, drips quality percentage composition 37% formaldehyde solution 285kg, drips to finish to be warming up to 90 ~ 95 DEG C, react with this understanding 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%, decompression vacuum pumping dehydration under heated condition, until temperature is about 90 DEG C, stop heating, add 40kg ethanol to stir and to obtain brown clarification 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
By Eugenol (82kg, 500mol) add synthesis reaction vessel with Platinic chloride 9g, stirring is warming up to 60 DEG C of left and right, by two decamethyl ten siloxanes (256.6kg, 352mol) drip in batches in reactor and keep temperature not higher than 80 DEG C, reaction proceeds to and after intensification phenomenon stops, continues to finish to make for 2 ~ 3 hours organosilicon modifier, productive rate 94% again.
Phenol 100kg, organosilicon modifier 10kg and sodium hydroxide 3.3kg are added to synthesis reaction vessel, heat up and stir, temperature rises to approximately 60 DEG C, drips quality percentage composition 37% formaldehyde solution 285kg, drips to finish to be warming up to 90 ~ 95 DEG C, react with this understanding 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%, decompression vacuum pumping dehydration under heated condition, until temperature is about 90 DEG C, stop heating, add 40kg ethanol to stir and to obtain brown clarification 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
By methyl eugenol (178kg, 1000mol) and isopropyl alcohol solution of chloroplatinic acid (platinum quality percentage composition 0.8%) 14.76g add synthesis reaction vessel, stirring is warming up to 60 DEG C of left and right, by 1,1,3,3-tetramethyl disiloxane (67kg, 500mol) drip in batches in reactor and keep temperature not higher than 80 DEG C, reaction proceeds to and after intensification phenomenon stops, continues to finish to make for 2 ~ 3 hours organosilicon modifier, productive rate 91% again.
Phenol 80kg, organosilicon modifier 10kg, sodium hydroxide 2.7kg are added to synthesis reaction vessel, heat up and stir, temperature rises to approximately 60 DEG C, drip massfraction 37% formaldehyde solution 100kg, drip to finish and be warming up to 80 ~ 85 DEG C of reaction 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%, decompression vacuum pumping dehydration under heated condition, until temperature is about 70 DEG C, stop heating, add 20kg ethanol to stir and to obtain brown clarification resin solution.The standby Effect of Organosilicon-modified Phenol-formaldehyde Resin of this legal system 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)。
Embodiment 8
By methyl eugenol (89kg, 500mol) add synthesis reaction vessel with Platinic chloride 9g, stirring is warming up to 60 DEG C of left and right, by two decamethyl ten siloxanes (256.6kg, 352mol) drip in batches in reactor and keep temperature not higher than 80 DEG C, reaction proceeds to and after intensification phenomenon stops, continues to finish to make for 2 ~ 3 hours organosilicon modifier, productive rate 95% again.
Phenol 100kg, organosilicon modifier 10kg and sodium hydroxide 3.3kg are added to synthesis reaction vessel, heat up and stir, temperature rises to approximately 60 DEG C, drips quality percentage composition 37% formaldehyde solution 285kg, drips to finish to be warming up to 90 ~ 95 DEG C, react with this understanding 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%, decompression vacuum pumping dehydration under heated condition, until temperature is about 90 DEG C, stop heating, add 40kg ethanol to stir and to obtain brown clarification 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 explanation of the nuclear magnetic data of embodiment 1 ~ 8 makes meets the structure shown in formula IV.
Reference example 1
Phenol 90kg and sodium hydroxide 2.7kg are added to synthesis reaction vessel, heat up and stir, temperature rises to approximately 60 DEG C, drip quality percentage composition 37% formaldehyde solution 100kg, and then be warming up to 90 ~ 95 DEG C of reaction 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%, decompression vacuum pumping dehydration under heated condition, until temperature is about 70 DEG C, stop heating, add the 20kg ethanol brown clarified liq resin solution that stirs to obtain.
Reference example 2
Phenol 110kg and sodium hydroxide 3.3kg are added to synthesis reaction vessel, heat up and stir, temperature rises to approximately 60 DEG C, drip quality percentage composition 37% formaldehyde solution 285kg, and then be warming up to 90 ~ 95 DEG C of reaction 130min, be neutralized to pH=7 with the hydrochloric acid of massfraction 5%, decompression vacuum pumping dehydration under heated condition, until temperature is about 90 DEG C, stop heating, add 40kg ethanol to stir and to obtain brown clarification resin solution.
Fig. 3 is the contrast of the resol performance for preparing of the heat-reactive phenolic resin prepared by this modifying agent and usual way, known 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.The comprehensive known organosilicon modifier of above data can effectively improve the property indices of Resol type resin.
Performance characterization method:
1. viscosity measurement liquid and solution shape resol viscosimetric analysis in accordance with HG/T 2712-95 chemical industry in China standard, measures 25 DEG C of temperature.
2. solid content is measured in accordance with GB GB-T2793-1995.
3. free phenol content is in accordance with GB GB-T 7130-1986 iodometric determination.
4. degradation temperature is after resin is fully solidified at 150 DEG C, to get the temperature rise rate heating with 10 DEG C/min with thermogravimetric analyzer under nitrogen atmosphere of 6-10mg sample, the temperature weightless 5% time.
Claims (5)
1. an organic-silicon-modified heat-reactive phenolic resin, is characterized in that, general structure is as shown in formula IV:
Resol1, Resol2 are positioned at R
1ortho position or contraposition, represent heat-reactive phenolic resin segmented structure;
The preparation method of described organic-silicon-modified heat-reactive phenolic resin is as follows:
Comprise: phenol and described organosilicon modifier are mixed, under alkaline condition, stirring is warming up to 55～60 DEG C, then splashes into formaldehyde solution, dropwises rear insulation 10～60min, be warming up to again 80～95 DEG C of reaction 100～150min, add acid to be neutralized to pH=7, under heated condition, decompression vacuum pumping dewaters until temperature is 60～80 DEG C, add stirring solvent even, make organic-silicon-modified heat-reactive phenolic resin;
Described phenol and the weight ratio of organosilicon modifier are 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;
The general structure of described organosilicon modifier is as follows:
In formula I and (IV), the integer that n is 1～50, R
1for hydroxyl or alkoxyl group, R
2, R
3be positioned at R
1ortho position or contraposition, be hydrogen, alkyl or alkoxyl group.
2. organic-silicon-modified heat-reactive phenolic resin according to claim 1, is characterized in that, described R
2for hydrogen, R
3for methyl or methoxy.
3. organic-silicon-modified heat-reactive phenolic resin according to claim 2, is characterized in that, described n=1 or 9, R
1for methoxyl group, R
3be positioned at R
1ortho position.
4. organic-silicon-modified heat-reactive phenolic resin according to claim 2, is characterized in that, described n=1,3 or 9, R
1for hydroxyl, R
3be positioned at R
1ortho position.
5. organic-silicon-modified heat-reactive phenolic resin according to claim 1, is characterized in that, described n=1, R
1for hydroxyl, R
3for hydrogen.
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| CN112851903B (en) * | 2021-01-12 | 2022-10-04 | 浙江多邦新材料有限公司 | Preparation method of organic silicon modified waterborne polyurethane and product thereof |
| CN114196024B (en) * | 2022-01-10 | 2023-05-30 | 万华化学集团股份有限公司 | Organosilicon modified phenolic resin and preparation method and application thereof |
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| CN101679642A (en) * | 2007-03-29 | 2010-03-24 | 莫门蒂夫性能材料股份有限公司 | Silicone compositions and methods for preparing them |
| CN101955596A (en) * | 2009-07-13 | 2011-01-26 | 上海赛星节能科技有限公司 | Preparation method of polydimethylsiloxane modified phenolic foam |
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| CN101679642A (en) * | 2007-03-29 | 2010-03-24 | 莫门蒂夫性能材料股份有限公司 | Silicone compositions and methods for preparing them |
| CN101955596A (en) * | 2009-07-13 | 2011-01-26 | 上海赛星节能科技有限公司 | Preparation method of polydimethylsiloxane modified phenolic foam |
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