CN103012704B - Preparation method of toughening thermoset phenolic resin - Google Patents
Preparation method of toughening thermoset phenolic resin Download PDFInfo
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- CN103012704B CN103012704B CN201110460622.9A CN201110460622A CN103012704B CN 103012704 B CN103012704 B CN 103012704B CN 201110460622 A CN201110460622 A CN 201110460622A CN 103012704 B CN103012704 B CN 103012704B
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- phenolic resin
- glycidyl ester
- acid glycidyl
- resol
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Abstract
The invention relates to a preparation method of toughening thermoset phenolic resin. In the preparation method, an ether bond is geneated through the addition reaction of the epoxy group of versatic acid glycidyl ester and the phenolic hydroxyl group of phenolic resin by taking the versatic acid glycidyl ester as a toughening agent, and a versatic acid ester ether chain is introduced into the phenolic resin, so that the toughening effect is realized. The toughening thermoset phenolic resin is prepared by adopting a subsection process which comprises the following steps of: firstly preparing high-ortho thermoplastic phenolic resin through phenol and formaldehyde; then adding the versatic acid glycidyl ester so that the phenolic hydroxyl group of the high-ortho thermoplastic phenolic resin without an active hydroxymethyl group is reacted with versatic acid glycidyl ester; and finally adding the formaldehyde to generate thermoset A-stage phenolic resin containing the hydroxymethyl group. The subsection process disclosed by the invention ensures that the versatic acid glycidyl ester is only subjected to addition with the phenolic hydroxyl group of the phenolic resin and prevented from being reacted with the hydroxymethyl group, thereby enhancing the toughness of the phenolic resin without influencing the subsequent curing property.
Description
Technical field
The present invention relates to a kind of preparation method of modified thermosetting phenolic resin, particularly take tertiary carbonic acid glycidyl ester as toughner, by the epoxy group(ing) on tertiary carbonic acid glycidyl ester and the phenolic hydroxyl group addition reaction on resol, generate ehter bond, tertiary carbon acid esters ether chain is introduced to resol, obtain the method for toughened thermosetting resol.
Background technology
Resol is the first kind resin material of synthetic in the world, and it has good acid resistance, mechanical property, resistance toheat, and because its raw material is easy to get, synthesizes conveniently, is still widely used at present.But its because of in molecular chain containing compared with multiple stiffness benzene ring structure, cause resol crisp, poor toughness, not shock resistance, limited the Application Areas of resol greatly.
In order to improve the toughness of resol, done a large amount of research both at home and abroad.The modification of resol is mainly physically modified and chemical modification.Chemical modification refers to and in resol building-up process or in curing molding process, adds the flexible molecule that contains the functional group that can react with phenolic hydroxyl group or the methylol of resol, make its with chemical bonding on the main chain or side chain of resol, thereby play toughening effect.Common chemical modifier has cashew nut oil, organosilicon, tung oil, urethane, flexible-epoxy, end carboxyl or terminal hydroxy group liquid polybutadiene, polyethers and polyester etc.
Zhang Yuan etc. (friction material matrix-phenolic resin modified research [J]. About Frp/cm, 1999,5:24-26), with bimaleimide resin and cashew nut shell oil addition reaction, then this prepolymer is carried out to condensation with phenolic aldehyde again, obtain cashew nut oil modified resol.Si Tuyue etc. (preparation of epoxidized soybean oil/phenol and anti-water sucting mechanism research [J]. colleges and universities' chemical engineering journal; 2011; 25 (1): 103-108) with epoxy soybean oil modified thermoplastic resol, obtain the novolac resin of plasticising.Tall winter equality (research of Phenolic Foam Plastic Toughening Modification with Flexible Epoxy Resin [J]. Henan chemical industry, 2006,23 (9): 22-23) under alkaline condition, by after phenol and formaldehyde reaction, add again flexible-epoxy to carry out modification, obtain toughness reinforcing resol.
Above-mentioned method of modifying is to utilize the active group on chemical modifier to react with methylol and phenolic hydroxyl group on resol, chemical modifier is connected on matrix resin, from playing toughness effect.But in modifying process, can consume the active methylol on resol, thereby affect the later stage curing performance of resol.Also there is people first by properties-correcting agent and phenol reactant, properties-correcting agent is connected on phenolic hydroxyl group and generates resol with formaldehyde reaction again, as Fang Ke etc. (Phenolic resin for high quality friction material [J]. Beijing University of Chemical Technology's journal, 1999,26 (4): 33-35) first use modification of flax oil phenol, and then with the phenol after modification, under acidic conditions, react the resol that generates modification of flax oil with formaldehyde solution, but because the change of phenol structure can affect itself and the reacting of formaldehyde, thereby be only applicable to the modification of novolac resin.
Summary of the invention
For fear of above defect, the invention provides a kind of preparation method of toughened thermosetting resol, adopt tertiary carbonic acid glycidyl ester to participate in polyreaction as toughner, become a part for resin, play the effect that improves the toughness of resin own.
A kind of preparation method of toughened thermosetting resol, it is characterized in that take that tertiary carbonic acid glycidyl ester is as toughner, by the epoxy group(ing) on tertiary carbonic acid glycidyl ester and the phenolic hydroxyl group addition reaction on resol, generate ehter bond, tertiary carbon acid esters ether chain is introduced to resol, and the mol ratio of described phenol and tertiary carbonic acid glycidyl ester is 1: 0.1-0.5.
Preparation method of the present invention adopts a minute segment process, and within described minute, segment process comprises the following steps:
(a) by phenol and formaldehyde 1.5-2 in molar ratio: 1 joins in reactor, and under acidic conditions, with divalent-metal ion catalysis, 80-90 ℃ of insulation reaction 1-3 hour, obtains high-ortho novolac resin;
(b) regulation system pH is to alkalescence, and adding with phenol mol ratio is 1: the tertiary carbonic acid glycidyl ester of 0.1-0.5,90-110 ℃ of insulation reaction 1-2 hour;
(c) system is cooled to 80-90 ℃, add formaldehyde, wherein the mol ratio of initial phenol and formaldehyde is 1: 0.5-1.1, total mol ratio of phenol and formaldehyde is 1: 1.2-1.6, after insulation reaction 1-2 hour, regulate pH to neutral, 80 ℃ of vacuum hydro-extraction 0.5-1 hour, obtain toughness reinforcing thermoset resole.
Described preparation method preferably comprises the following steps: 94g phenol and 72g formalin are joined in reactor, and after stirring, regulation system pH to 5.1, adds 8.8g zinc acetate, is warming up to 85 ℃, and insulation reaction 2 hours, obtains high adjacent position phenolic resin; Regulation system pH to 8.0, adds 85g toughner tertiary carbonic acid glycidyl ester, is warming up to 110 ℃, and insulation reaction is after 2 hours; Be cooled to 85 ℃, add 38g formalin, insulation reaction 1 hour; Regulation system pH is to neutral, and vacuum hydro-extraction 1 hour, obtains toughened thermosetting resol.
Toughner of the present invention is tertiary carbonic acid glycidyl ester, and its epoxy group(ing) has very strong reactivity, and structural formula as shown in Figure 1.The epoxy group(ing) of tertiary carbonic acid glycidyl ester can react with phenolic hydroxyl group, becomes the integral part of resol, and curling structure provides toughening effect, and reaction formula as shown in Figure 2.The aliphatics characteristic of the tertiary monocarboxylic acid group of tertiary carbonic acid glycidyl ester improves resin weathering resistance, and the tertiary monocarboxylic acid group of suspension can also reduce viscosity, increases self-plasticizing action.In addition, its toxicity is little, almost non-stimulated to human body skin.
The present invention be take tertiary carbonic acid glycidyl ester as intrinsic toughening agent, takes a minute segment process, first, under acidic conditions, under divalent-metal ion catalysis, prepares high adjacent position phenolic resin; Then under alkaline condition, add tertiary carbonic acid glycidyl ester, the epoxy group(ing) of tertiary carbonic acid glycidyl ester is reacted with on the phenolic hydroxyl group of high adjacent position phenolic resin, makes, on its phenolic hydroxyl group that is bonded to resin, to improve its toughness; Finally add formaldehyde, generate the thermoset resole that contains methylol.Such preparation technology compares with one-step synthesis technique and has guaranteed that tertiary carbon acid esters only reacts with the phenolic hydroxyl group of phenol, has avoided it react and affect its later stage curing performance with the methylol on resol, and reaction principle as shown in Figure 3.
Compared with prior art, the present invention has following outstanding feature and advantage: the present invention be take tertiary carbonic acid glycidyl ester as toughner, reacts with phenolic hydroxyl group, becomes the integral part of resol.The aliphatics characteristic of tertiary monocarboxylic acid group improves resin weathering resistance, and the tertiary monocarboxylic acid group of suspension can also reduce viscosity, increases self-plasticizing action, and meanwhile, tertiary carbonic acid glycidyl ester toxicity is little, almost non-stimulated to human body skin.Take a minute segment process, first synthetic high adjacent position phenolic resin, then react with the phenolic hydroxyl group on the high adjacent position phenolic resin of tertiary carbonic acid glycidyl ester and non-activity methylol, make it be bonded on resin completely, finally again with formaldehyde reaction, generate the thermoset resole contain methylol.Such preparation technology has guaranteed that tertiary carbon acid esters only reacts with the phenolic hydroxyl group of phenol, has improved the toughness of resol, has avoided again reacting with methylol on resol and affects its later stage curing performance.The tensile strength of plasticizing phenol formaldehyde prepared by the present invention and flexural strength have had significantly and have improved than unmodified resol respectively.
Accompanying drawing explanation
Fig. 1 is the structural formula of toughner tertiary carbonic acid glycidyl ester, wherein, R1, R2 is highly branched alkyl, altogether containing 4 carbon atoms.
Fig. 2 is the epoxy group(ing) of tertiary carbonic acid glycidyl ester and the reaction formula of phenolic hydroxyl group.
Fig. 3 is preparation technology's of the present invention reaction principle.
Embodiment
Below, by specific specific examples explanation embodiments of the present invention, be to further illustrate of the present invention, rather than limit the scope of the invention.
Embodiment 1
94g phenol and 72g formalin are joined in reactor, and after stirring, regulation system pH to 5.1, adds 8.8g zinc acetate, is warming up to 85 ℃, and insulation reaction 2 hours, obtains high adjacent position phenolic resin; Regulation system pH to 8.0, adds 45g toughner tertiary carbonic acid glycidyl ester, is warming up to 110 ℃, and insulation reaction is after 2 hours; Be cooled to 85 ℃, add 40g formalin, insulation reaction hours 2; Regulation system pH is to neutral, and vacuum hydro-extraction 1 hour, obtains toughened thermosetting resol.The viscosity of resin is 6020mPa.s, gelation time 82s, and tensile strength is 23.67MPa, flexural strength 39.89MPa.
Embodiment 2
94g phenol and 72g formalin are joined in reactor, and after stirring, regulation system pH to 5.1, adds 8.8g zinc acetate, is warming up to 85 ℃, and insulation reaction 2 hours, obtains high adjacent position phenolic resin; Regulation system pH to 8.0, adds 60g toughner tertiary carbonic acid glycidyl ester, is warming up to 110 ℃, and insulation reaction is after 2 hours; Be cooled to 85 ℃, add 45g formalin, insulation reaction 1.5 hours; Regulation system pH is to neutral, and vacuum hydro-extraction 1 hour, obtains toughened thermosetting resol.The viscosity of resin is 5800mPa.s, gelation time 80s, and tensile strength is 24.67MPa, flexural strength 42.35MPa.
Embodiment 3
94g phenol and 72g formalin are joined in reactor, and after stirring, regulation system pH to 5.1, adds 8.8g zinc acetate, is warming up to 85 ℃, and insulation reaction 2 hours, obtains high adjacent position phenolic resin; Regulation system pH to 8.0, adds 85g toughner tertiary carbonic acid glycidyl ester, is warming up to 110 ℃, and insulation reaction is after 2 hours; Be cooled to 85 ℃, add 38g formalin, insulation reaction 1 hour; Regulation system pH is to neutral, and vacuum hydro-extraction 1 hour, obtains toughened thermosetting resol.The viscosity of resin is 5760mPa.s, gelation time 95s, and tensile strength is 25.06MPa, flexural strength 44.78MPa.
Contrast experiment
94g phenol and 72g formalin are joined in reactor, and after stirring, regulation system pH to 5.1, adds 8.8g zinc acetate, is warming up to 85 ℃, and insulation reaction 2 hours, obtains high adjacent position phenolic resin; Regulation system pH to 8.0, adds 45g toughner tertiary carbonic acid glycidyl ester, is warming up to 110 ℃, and insulation reaction is after 2 hours; Be cooled to 85 ℃, add 40g formalin, insulation reaction hours 2; Regulation system pH is to neutral, and vacuum hydro-extraction 1 hour, obtains toughened thermosetting resol.The viscosity of resin is 4800mPa.s, gelation time 80s, and tensile strength is 21.07MPa, flexural strength 37.54MPa.
From the data of embodiment and simultaneous test, the tensile strength of plasticizing phenol formaldehyde prepared by the present invention and flexural strength have approximately improved 20% and 18% than unmodified resol respectively.Wherein embodiment 3 effects are best.
Claims (2)
1. the preparation method of a toughened thermosetting resol, it is characterized in that take that tertiary carbonic acid glycidyl ester is as toughner, by the epoxy group(ing) on tertiary carbonic acid glycidyl ester and the phenolic hydroxyl group addition reaction on resol, generate ehter bond, tertiary carbon acid esters ether chain is introduced to resol
Described preparation method adopts a minute segment process, and within described minute, segment process comprises the following steps:
(a) by phenol and formaldehyde in molar ratio 1.2-2:1 join in reactor, under acidic conditions, with divalent-metal ion catalysis, 80-90 ℃ of insulation reaction 1-3 hour, obtains high-ortho novolac resin;
(b) regulation system pH is to alkalescence, the tertiary carbonic acid glycidyl ester that to add with phenol mol ratio be 1:0.1-0.5,90-110 ℃ of insulation reaction 1-2 hour;
(c) system is cooled to 80-90 ℃, add formaldehyde, wherein the mol ratio of initial phenol and formaldehyde is 1:0.5-1.1, total mol ratio of phenol and formaldehyde is 1:1.2-1.6, after insulation reaction 1-2 hour, regulate pH to neutral, 80 ℃ of vacuum hydro-extraction 0.5-1 hour, obtain toughness reinforcing thermoset resole.
2. the preparation method of toughened thermosetting resol according to claim 1, it is characterized in that described preparation method comprises the following steps: 94g phenol and 72g formalin are joined in reactor, after stirring, regulation system pH to 5.1, add 8.8g zinc acetate, be warming up to 85 ℃, insulation reaction 2 hours, obtains high adjacent position phenolic resin; Regulation system pH to 8.0, adds 85g toughner tertiary carbonic acid glycidyl ester, is warming up to 110 ℃, and insulation reaction is after 2 hours; Be cooled to 85 ℃, add 38g formalin, insulation reaction 1 hour; Regulation system pH is to neutral, and vacuum hydro-extraction 1 hour, obtains toughened thermosetting resol.
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| CN104327228B (en) * | 2014-11-26 | 2016-06-22 | 沈阳化工大学 | A kind of Ni modified thermosetting phenolic resin preparation method |
| CN105694353B (en) * | 2016-02-02 | 2018-09-07 | 青岛科技大学 | A kind of toughened thermosetting phenol resin composition and preparation method thereof |
| CN106751436B (en) * | 2016-11-09 | 2019-06-18 | 上海欧亚合成材料有限公司 | Phenolaldehyde moulding compound for thin-wall construction |
| CN107573470B (en) * | 2017-09-18 | 2020-05-12 | 航天材料及工艺研究所 | Modified thermosetting phenolic resin and preparation method thereof |
| CN108047404B (en) * | 2017-12-11 | 2020-12-22 | 山东非金属材料研究所 | Water-based self-dispersion thermosetting phenolic resin and preparation method thereof |
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| CN1651542A (en) * | 2005-01-07 | 2005-08-10 | 武汉理工大学 | Epoxy resin binding agent for sand paper and its preparation method |
| CN102276776A (en) * | 2011-06-29 | 2011-12-14 | 山东圣泉化工股份有限公司 | Production method of butylated bisphenol A formaldehyde resin |
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| CN1651542A (en) * | 2005-01-07 | 2005-08-10 | 武汉理工大学 | Epoxy resin binding agent for sand paper and its preparation method |
| CN102276776A (en) * | 2011-06-29 | 2011-12-14 | 山东圣泉化工股份有限公司 | Production method of butylated bisphenol A formaldehyde resin |
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