CN106565923A - Silicon-containing epoxy anacardol-group phenolic resin, and preparation method and application of silicon-containing epoxy anacardol-group phenolic resin - Google Patents
Silicon-containing epoxy anacardol-group phenolic resin, and preparation method and application of silicon-containing epoxy anacardol-group phenolic resin Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Abstract
The invention discloses silicon-containing epoxy anacardol-group phenolic resin, and a preparation method and an application of the silicon-containing epoxy anacardol-group phenolic resin. First, epoxidation anacardol and vinyl bromides, under a salt or alkali existence condition, react and generate alkylated epoxy anacardol; furthermore, the alkylated epoxy anacardol is taken as a raw material, and reacts with a silane coupling agent under a catalyst existence condition, and a silicon-containing epoxy anacardol-group chemical compound is prepared; by mass, 100-300 parts of carbolic acid, 50-180 parts of paraformaldehyde, 1-25 parts of the above silicon-containing epoxy anacardol-group chemical compound serve as reactants, an alkaline catalyst is added for reaction, and the silicon-containing epoxy anacardol-group phenolic resin is prepared. A surfactant, a foaming agent and a curing agent are sequentially added to the silicon-containing epoxy anacardol-group phenolic resin, and a silicon-containing epoxy anacardol-group phenolic foam insulation material is prepared. The mechanical property and the thermostability of the prepared silicon-containing epoxy anacardol-group phenolic foam insulation material is prepared are improved obviously.
Description
Technical field
The present invention relates to a kind of biomass-based phenolic resin and foam and preparation method thereof, relate generally to siliceous epoxy biological
Matter glycolylate and preparation method thereof and the application in phenolic resin and foamed plastics.
Background technology
Phenolic foam is the new ingrain fireproofing insulation material of the class for growing up in recent years, with thermal conductivity factor
It is excellent that the burning hot decomposition of low, chance does not discharge pernicious gas, dimensionally stable, easy-formation processing, resistance to chemical attack and preferable durability etc.
Gesture and gradually receive significant attention.The primary raw material for preparing phenolic foam is phenolic resin, and traditional phenolic foam
It is by phenolic resin in the presence of curing agent, foaming agent, surfactant and other auxiliary agents, while being foamed, being solidified and made
Standby.Because being only connected by methylene between aromatic core, this structure causes phenyl ring density in phenol formaldehyde foam to phenolic resin after solidification
Excessive, intramolecular lattice chain is too short, rotary freedom is less so that phenolic foam to there is elongation percentage low, hardness is big, resistance to
Impact is poor, the problems such as rate of slag falling is high, limits its application and fast-developing.Therefore phenolic resin and foam are modified and are ground
Study carefully to reduce its fragility, improve its toughness, with certain theoretical and realistic meaning.Want with the extension of application and to material
The raising asked, traditional phenol formaldehyde foam cannot meet the requirement of commercial Application, the study on the modification of phenol formaldehyde foam is met the tendency of and
It is raw.The modified main purpose of phenolic foam is the toughness and mechanical strength of reinforced nylon66, while as far as possible unobvious
Destruction its high temperature resistant, the performance of anti-flaming thermal-insulation.
Both at home and abroad substantial amounts of research has been done in the application to organosilicon and its graft polymers in phenolic resin, and achieves
Some progress, but most document and patent research its application in thermoplastic phenolic resin, in thermosetting phenolic
Research in resin and phenol formaldehyde foam is very few.By organosilicon and its graft polymers to thermosetting phenolic resin and phenol formaldehyde foam
Modifying plastics, can improve the properties of product, and the past is open with regard to organosilicon and its graft polymers modified heat convertible phenol
Urea formaldehyde and foamed plastics mainly adopt two kinds of approach：One is that modified, phenolic resin appearance prepared by the method is realized by blending
Easily it is layered, organosilicon and phenolic compatible are poor, so as to affect the mechanical performance of product；Another is to add response type silicones
Enter in phenolic system, Chinese patent CN102675572B is carried out using a kind of organosilicon modifier to thermosetting phenolic resin
It is modified, the heat endurance of resin is improve, but the technique uses formalin, reaction to need the reduced vacuum to be dehydrated after terminating, and
Stirring solvent is added, thermosetting resin can be obtained, technics comparing is complicated, increased manufacturing cost, and has waste water to produce.It is Chinese special
Sharp CN105254828A discloses a kind of eight phenolic hydroxyl groups polyhedral oligomeric silsesquioxane hybrid phenol-formaldehyde resin and preparation method thereof, should
Method solves dispersion problem of the organosilicon in phenolic resin, and the resin heat endurance of preparation increases, but this
Eight phenolic hydroxyl group polyhedral oligomeric silsesquioxanes of bright preparation need to use ice-water bath, and need to be passed through inert gas and protected, and close
Sufficiently complex into technique, while carrying out reaction using formalin and phenol prepares resin, reaction needs reduced vacuum to take off after terminating
Water, can obtain thermosetting resin, and process is sufficiently complex.
In addition, being all stone currently used for the organosilicon and its graft polymers of modified thermosetting phenolic resin and foamed plastics
Oil-based products, and the research with regard to forestry (product) silicon containing biomass base modified thermosetting phenolic resin and foamed plastics rarely has report
Road.
What the problems such as with people's environmental pollution, crisis of resource recognized deepens continuously, biomass natural polymer it is rich
The characteristics of rich resource and high added value, is also increasingly subject to pay attention to, and finds renewable forestry biomass resource to replace oil product day
Benefit obtains the concern of people.Anacardol is a kind of natural phenolic compound, containing unsaturated C15Long carbon chain, it is wide so as to make it have
General modified basis, can be as the substitute of petrochemical material, in coating, strength mixture, friction material, pluronic polymer and other height
Molecular material field is widely used.In recent years, researcher replaced the mode of phenol to anacardol, how to improve anacardol
Replacement amount, to prepare phenolic resin and foamed plastics substantial amounts of research has been carried out, and is polymerized with organosilicon grafting synthesizing organo-silicon
There is not been reported in the document of thermosetting phenolic resin and foam applications application for thing.
The present invention utilizes the distinctive structural system of anacardol, and organosilicon is grafted on anacardol molecular structure, and synthesis contains
Silicon epoxy cashew nut phenol-based compounds, and be added in phenolic resin so that siliceous epoxy cashew nut phenol-based compounds and phenolic resin
In hydroxyl carry out ring-opening reaction so as to possess the compatibility good with phenolic resin system, form homogeneous with phenolic resin
Phase, element silicon and the distinctive flexible chain structure of anacardol are introduced in phenolic resin simultaneously, improve phenolic foam extension
Rate is low, the defect that rate of slag falling is high, and improves the heat endurance of phenolic resin and foamed plastics.The present invention is not only anacardol
Higher value application provides new way, and theory and technology basis is established in the also exploitation for phenolic aldehyde thermal insulation material new capability.
The content of the invention
The technical problem of solution：The invention provides a kind of siliceous epoxy cashew nut phenolic group phenolic resin and preparation method thereof and
Using making the hydroxyl in siliceous epoxy cashew nut phenol-based compounds and phenolic resin carry out ring-opening reaction so as to possess and phenolic resin
The good compatibility of system, with phenolic resin homogeneous phase is formed, and solves physical blending organosilicon dispersiveness in phenolic resin
Problem, has obtained dispersed more preferable, more uniform phenolic resin, and improves phenolic foam intensity in prior art
The defects such as low, poor toughness, obtained siliceous epoxy cashew nut phenolic group foamed plastics has very good mechanical properties and heat resistance.
Technical scheme：The preparation method of siliceous epoxy cashew nut phenolic group phenolic resin, step is：(1) siliceous epoxy anacardol
The preparation of basic ring compound：First, under conditions of salt or alkali are present, epoxy anacardol and bromo alkene react 7 in 30～70 DEG C
～24h, generates alkylation epoxy anacardol, wherein the epoxy anacardol is 1 with the mol ratio of the alkali or salt:1～1:4；
The bromo alkene is 1 with the mol ratio of epoxy anacardol:1～1:3；Secondly, under conditions of catalyst is present, will be obtained
Alkylation epoxy anacardol reacts 1～8h with silane coupler at 50～80 DEG C, generates siliceous epoxy anacardol basic ring compound, its
Middle catalyst amount is be alkylated epoxy anacardol quality 0.5%～1.5%, alkylation epoxy anacardol and silane coupler
Mol ratio be 2:1～1:1, the catalyst is chloroplatinic acid；(2) preparation of siliceous epoxy cashew nut phenolic group phenolic resin：By than
Example, with the phenol of 100～300 mass parts, the paraformaldehyde of 50～180 mass parts, the above-mentioned siliceous epoxy cashew nut of 1～25 mass parts
Phenolic group cyclisation thing is reactant, and the base catalyst reaction for adding effective dose is obtained siliceous epoxy cashew nut phenolic group phenolic resin.
Above-mentioned bromo alkene is bromo butylene or bromo propylene.
Above-mentioned salt or alkali are sodium carbonate, potassium carbonate, NaOH or potassium hydroxide.
Above-mentioned silane coupler is pentamethyl disiloxane, tetramethyl disiloxane or trimethoxy silane.
Above-mentioned base catalyst is at least one in NaOH, barium hydroxide, triethylamine or potassium hydroxide.
Preferably, it is above-mentioned by mass parts by phenol, paraformaldehyde, siliceous epoxy anacardol basic ring compound mixing after, add
Base catalyst adjusts pH value 7.5～11, is warming up to 80～95 DEG C, carries out 2～4h of isothermal reaction.
The siliceous epoxy cashew nut phenolic group phenolic resin that said method is prepared.
Application of the siliceous epoxy cashew nut phenolic group phenolic resin in foamed plastics is prepared, in siliceous epoxy cashew nut phenolic group phenolic aldehyde
In resin, add surfactant, foaming agent and curing agent to stir, in pouring mould into, and heated in 75～85 DEG C
Curing molding, is obtained siliceous epoxy cashew nut phenolic group phenol formaldehyde foam；Wherein, each material addition example in mass ratio is, siliceous epoxy
100 parts of cashew nut phenolic group phenolic resin, 1～15 part of surfactant, 5～15 parts of foaming agent, 1～20 part of curing agent.
The addition of above-mentioned substance is respectively siliceous 100 parts of epoxy cashew nut phenolic group phenolic resin, and 10 parts of surfactant is sent out
15 parts of infusion, 15 parts of curing agent.
Above-mentioned surfactant is in Tween-60, Tween-80, polysiloxane-based or poly- silica vinyl surfactant
At least one；The foaming agent is any one in petroleum ether, pentane, isopentane, pentamethylene, normal butane or dichloromethane
Kind；It is (30～20) that the curing agent is phosphoric acid, p-methyl benzenesulfonic acid and water in mass ratio:(100～90):The mixing of (20～30)
Acid.
Beneficial effect：1st, make siliceous epoxy cashew nut phenol-based compounds and the hydroxyl in phenolic resin carry out ring-opening reaction so as to
Possess the compatibility good with phenolic resin system, with phenolic resin homogeneous phase is formed, solve physical blending organosilicon in phenol
Dispersion problem in urea formaldehyde, has obtained dispersed more preferable, more uniform phenol-formaldehyde resin modified.
2nd, Si-O bond structures are introduced in phenolic resin molecule, therefore prepared phenolic resin and phenol formaldehyde foam are heat-resisting
Property it is high.
3rd, the present invention introduces the preferable fat chain structure of anacardol pliability in phenol formaldehyde foam molecular structure, improves phenolic aldehyde
Foamed plastics elongation percentage is low, the defect that rate of slag falling is high.
4th, anacardol is renewable resource, abundance and low cost.
Description of the drawings
Fig. 1 is the infrared spectrum of the siliceous epoxy cashew nut phenol-based compounds of embodiment 1.
From the infrared spectrum of the siliceous epoxy cashew nut phenol-based compounds of Fig. 1：3375cm-1Epoxy anacardol-OH groups shake
Dynamic peak disappears, and illustrates that epoxy anacardol alkylated reaction is more complete.1255cm-1Locate the stretching vibration peak for Si-C, 1034cm-1And 838cm-1For the stretching vibration peak of Si-O-Si, illustrate that the organosiloxane that hydrogen is blocked is had been attached on epoxy anacardol.
Specific embodiment
Following examples further illustrate present disclosure, but should not be construed as limiting the invention.Without departing substantially from
In the case of spirit of the invention and essence, the modification made to the inventive method, step or condition and replacement belong to the present invention
Scope.
This raw material be all it is commercially available, if being all mass parts without specializing in following examples.
Embodiment 1
(1) preparation of siliceous epoxy cashew nut phenol-based compounds：11g epoxy anacardols, 18g carbonic acid are added in reaction bulb
Sodium, 4g 2- bromopropenes, 50mL acetone reacts 20h in 55 DEG C, generates alkylation epoxy anacardol；Alkylation epoxy anacardol 7g
Under conditions of catalyst chloroplatinic acid is present, pentamethyl disiloxane 3g is added dropwise, in 50 DEG C 8h is reacted, obtain siliceous epoxy cashew nut
Phenol-based compounds；
(2) preparation of siliceous epoxy cashew nut phenolic group phenolic resin：In proportion, with the phenol of 100 mass parts, 55 mass parts
The siliceous epoxy cashew nut phenol-based compounds of paraformaldehyde, 1 mass parts are reactant, add 20wt.% sodium hydroxide solutions to adjust body
It is that pH is 8～9,85 DEG C of reaction 4h, siliceous epoxy cashew nut phenolic group phenolic resin is obtained；
(3) preparation of siliceous epoxy cashew nut phenolic group phenol formaldehyde foam：By mass parts, in 100 parts of siliceous epoxy cashew nut phenolic group phenol
In urea formaldehyde, be directly added into 5 parts of Tween-80s, 5 parts of silicone oil, 10 parts of pentanes and 15 parts of curing agent (phosphoric acid, p-methyl benzenesulfonic acid and
The mass ratio of water is 25:85:25), stir, in pouring mould into, and the shaping that is heating and curing is carried out with 75 DEG C, siliceous ring is obtained
Oxygen cashew nut phenolic group phenol formaldehyde foam.
Embodiment 2
(1) preparation of siliceous epoxy cashew nut phenol-based compounds：30g epoxy anacardols, 25g carbonic acid are added in reaction bulb
Potassium, 12g 3- bromopropenes, 150mL methyl alcohol reacts 15h in 65 DEG C, generates alkylation epoxy anacardol；Alkylation epoxy anacardol
25g is added dropwise tetramethyl disiloxane 4g under conditions of the presence of catalyst chloroplatinic acid, and in 60 DEG C 7h is reacted, and obtains siliceous epoxy
Cashew nut phenol-based compounds；
(2) preparation of siliceous epoxy cashew nut phenolic group phenolic resin：In proportion, with the phenol of 100 mass parts, 50 mass parts
Paraformaldehyde, adds barium hydroxide regulation system pH to be 9～10,85 DEG C of reaction 1h, adds the siliceous epoxy cashew nut phenolic group of 3 mass parts
Compound is reactant, and in 90 DEG C 50min is reacted, and is then cooled to 80 DEG C of reaction 2h, and siliceous epoxy cashew nut phenolic group phenolic aldehyde is obtained
Resin；
(3) preparation of siliceous epoxy cashew nut phenolic group phenol formaldehyde foam：By mass parts, in 100 parts of siliceous epoxy cashew nut phenolic group phenol
In urea formaldehyde, 4 parts of Tween-60s, 5 parts of silicone oil, 8 parts of pentanes and 13 parts of curing agent (phosphoric acid, p-methyl benzenesulfonic acid and water are directly added into
Mass ratio be 20:80:35), stir, in pouring mould into, and the shaping that is heating and curing is carried out with 80 DEG C, siliceous epoxy is obtained
Cashew nut phenolic group phenol formaldehyde foam.
Embodiment 3
(1) preparation of siliceous epoxy cashew nut phenol-based compounds：51g epoxy anacardols, 25g hydroxides are added in reaction bulb
Sodium, 60g 4- bromobutenes, 250mL methyl alcohol reacts 24h in 60 DEG C, generates alkylation epoxy anacardol；Alkylation epoxy anacardol
43g is added dropwise trimethoxy silane 16g under conditions of the presence of catalyst chloroplatinic acid, and in 70 DEG C 3h is reacted, and obtains siliceous epoxy waist
Fruit phenol-based compounds；
(2) preparation of siliceous epoxy cashew nut phenolic group phenolic resin：In proportion, with the phenol of 300 mass parts, 175 mass parts
Paraformaldehyde, add triethylamine regulation system pH to be 9～10,80 DEG C of reaction 1.5h, add the siliceous epoxy cashew nut of 24 mass parts
Phenol-based compounds are reactant, and in 95 DEG C 25min is reacted, and are then cooled to 85 DEG C of reaction 1h, and siliceous epoxy cashew nut phenolic group is obtained
Phenolic resin；
(3) preparation of siliceous epoxy cashew nut phenolic group phenol formaldehyde foam：By mass parts, in 100 parts of siliceous epoxy cashew nut phenolic group phenol
In urea formaldehyde, 4 parts of APESs -10,4 parts of silicone oil, 10 parts of pentanes and 8 parts of curing agent are directly added into (phosphoric acid, right
The mass ratio of toluenesulfonic acid and water is 35:82:25), stir, in pouring mould into, and the shaping that is heating and curing carried out with 85 DEG C,
Siliceous epoxy cashew nut phenolic group phenol formaldehyde foam is obtained.
Embodiment 4
(1) preparation of siliceous epoxy cashew nut phenol-based compounds：51g epoxy anacardols, 26g hydroxides are added in reaction bulb
Potassium, the bromo- 2- butylene of 70g 2-, 250mL acetone reacts 10h in 55 DEG C, generates alkylation epoxy anacardol；Alkylation epoxy waist
Fruit phenol 40g is added dropwise tetramethyl diphenyl trisiloxanes trimethoxy silane 22g under conditions of the presence of catalyst chloroplatinic acid, in
80 DEG C of reaction 4h, obtain siliceous epoxy cashew nut phenol-based compounds；
(2) preparation of siliceous epoxy cashew nut phenolic group phenolic resin：In proportion, with the phenol of 200 mass parts, 115 mass parts
Paraformaldehyde, the siliceous epoxy cashew nut phenol-based compounds of 20 mass parts add potassium hydroxide regulation system pH to be 10～11,90 DEG C
Reaction 1.5h, is then cooled to 85 DEG C of reaction 45min, and siliceous epoxy cashew nut phenolic group phenolic resin is obtained；
(3) preparation of siliceous epoxy cashew nut phenolic group phenol formaldehyde foam：By mass parts, in 100 parts of siliceous epoxy cashew nut phenolic group phenol
In urea formaldehyde, 5 parts of sorbester p17s, 5 parts of silicone oil, 10 parts of pentanes and 10 parts of curing agent (phosphoric acid, p-methyl benzenesulfonic acid and water are directly added into
Mass ratio be 35:75:25), stir, in pouring mould into, and the shaping that is heating and curing is carried out with 80 DEG C, siliceous epoxy is obtained
Cashew nut phenolic group phenol formaldehyde foam.
Comparative example 1
By mass parts, in 100 parts of resols, 5 parts of Tween-80s, 5 parts of silicone oil, 10 parts of pentanes are directly added into
(mass ratio of phosphoric acid, p-methyl benzenesulfonic acid and water is 25 with 15 parts of curing agent:85:25), stir, in pouring mould into, and with
75 DEG C carry out the shaping that is heating and curing, and pure phenol formaldehyde foam is obtained.
Comparative example 2
By mass parts, in 100 parts of resols, be directly added into 5 parts of sorbester p17s, 5 parts of silicone oil, 10 parts of pentanes and
(mass ratio of phosphoric acid, p-methyl benzenesulfonic acid and water is 35 to 10 parts of curing agent:75:25), stir, in pouring mould into, and with 80
DEG C the shaping that is heating and curing is carried out, pure phenol formaldehyde foam is obtained.
The siliceous epoxy cashew nut phenolic group phenolic foam properties of product of table 1 (method of testing is with reference to national standard) foam density
For 50 ± 5Kg/m3
Measure shows：The siliceous epoxy cashew nut base phenolic foam sample that the present invention is prepared, with good power
Learn performance and heat endurance；0.289～0.373MPa of bending strength, significantly larger than pure phenolic foam；Thermal weight loss is maximum
Decomposition temperature during speed and 800 DEG C it is residual it is heavy be all higher than pure phenolic foam sample.
The present invention makes full use of the distinctive structural system of biomass resource anacardol, makes siliceous epoxy cashew nut phenol-based compounds
Ring-opening reaction is carried out so as to possess the compatibility good with phenolic resin system, with the hydroxyl in phenolic resin with phenolic resin shape
Into homogeneous phase, physical blending organosilicon dispersion problem in phenolic resin is solved, obtained dispersed more preferable, more uniformly
Phenol-formaldehyde resin modified.Si-O bond structures, therefore prepared phenolic resin and phenol formaldehyde foam are introduced in phenolic resin molecule
Heat resistance is high.Introduce the preferable fat chain structure of anacardol pliability in phenol formaldehyde foam molecular structure simultaneously, improve phenolic aldehyde bubble
Foam plastics elongation percentage is low, the defect that rate of slag falling is high.
Claims (10)
1. the preparation method of siliceous epoxy cashew nut phenolic group phenolic resin, it is characterised in that step is：
（1）The preparation of siliceous epoxy anacardol basic ring compound：First, under conditions of salt or alkali are present, epoxy anacardol and bromine
React 7 ~ 24 h in 30 ~ 70 DEG C for alkene, generate alkylation epoxy anacardol, wherein the epoxy anacardol and the alkali or
The mol ratio of salt is 1:1~1:4；The bromo alkene is 1 with the mol ratio of epoxy anacardol:1~1:3；Secondly, deposit in catalyst
Under the conditions, obtained alkylation epoxy anacardol and silane coupler are reacted into 1 ~ 8 h at 50 ~ 80 DEG C, generates siliceous ring
Oxygen cashew nut phenol-based compounds, wherein catalyst amount are be alkylated epoxy anacardol quality 0.5% ~ 1.5%, are alkylated epoxy waist
Fruit phenol is 2 with the mol ratio of silane coupler:1~1:1, the catalyst is chloroplatinic acid；
（2）The preparation of siliceous epoxy cashew nut phenolic group phenolic resin：In proportion, with the phenol of 100 ~ 300 mass parts, 50 ~ 180 mass
The paraformaldehyde of part, the above-mentioned siliceous epoxy cashew nut phenol-based compounds of 1 ~ 25 mass parts are reactant, and the alkalescence for adding effective dose is urged
Agent reaction is obtained siliceous epoxy cashew nut phenolic group phenolic resin.
2. the preparation method of siliceous epoxy cashew nut phenolic group phenolic resin according to claim 1, it is characterised in that the bromo
Alkene is bromo butylene or bromo propylene.
3. the preparation method of siliceous epoxy cashew nut phenolic group phenolic resin according to claim 1, it is characterised in that the salt or
Alkali is sodium carbonate, potassium carbonate, NaOH or potassium hydroxide.
4. the preparation method of siliceous epoxy cashew nut phenolic group phenolic resin according to claim 1, it is characterised in that the silane
Coupling agent is pentamethyl disiloxane, tetramethyl disiloxane or trimethoxy silane.
5. the preparation method of siliceous epoxy cashew nut phenolic group phenolic resin according to claim 1, it is characterised in that the alkalescence
Catalyst is at least one in NaOH, barium hydroxide, triethylamine or potassium hydroxide.
6. the preparation method of siliceous epoxy cashew nut phenolic group phenolic resin according to claim 1, it is characterised in that described by matter
After amount part is by phenol, paraformaldehyde, the mixing of siliceous epoxy cashew nut phenol-based compounds, add base catalyst adjust pH value 7.5 ~
11,80 ~ 95 DEG C are warming up to, carry out 2 ~ 4h of isothermal reaction.
7. the siliceous epoxy cashew nut phenolic group phenolic resin that the arbitrary methods described of claim 1 ~ 6 is prepared.
8. application of the siliceous epoxy cashew nut phenolic group phenolic resin in foamed plastics is prepared described in claim 7, it is characterised in that
In siliceous epoxy cashew nut phenolic group phenolic resin, add surfactant, foaming agent and curing agent to stir, pour mould into
In, and the shaping that is heating and curing is carried out in 75 ~ 85 DEG C, siliceous epoxy cashew nut phenolic group phenol formaldehyde foam is obtained；Wherein, each material addition
Example in mass ratio is that siliceous 100 parts of epoxy cashew nut phenolic group phenolic resin, 1 ~ 15 part of surfactant, 5 ~ 15 parts of foaming agent solidifies
1 ~ 20 part of agent.
9. application according to claim 8, it is characterised in that the addition of the material is respectively siliceous epoxy anacardol
100 parts of base phenolic resin, 10 parts of surfactant, 15 parts of foaming agent, 15 parts of curing agent.
10. application according to claim 8, it is characterised in that the surfactant is Tween-60, Tween-80, poly- silicon
At least one in oxygen alkanes or poly- silica vinyl surfactant；The foaming agent be petroleum ether, pentane, isopentane,
Any one in pentamethylene, normal butane or dichloromethane；The curing agent is that phosphoric acid, p-methyl benzenesulfonic acid and water are in mass ratio
（30~20）:（100~90）:（20~30）Mixed acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610951681.9A CN106565923B (en) | 2016-11-02 | 2016-11-02 | Siliceous epoxy cashew nut phenolic group phenolic resin and its preparation method and application |
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| CN201610951681.9A CN106565923B (en) | 2016-11-02 | 2016-11-02 | Siliceous epoxy cashew nut phenolic group phenolic resin and its preparation method and application |
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| CN106565923A true CN106565923A (en) | 2017-04-19 |
| CN106565923B CN106565923B (en) | 2018-10-30 |
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| CN115785612A (en) * | 2022-12-14 | 2023-03-14 | 广西北海翰鑫木业科技有限公司 | Quartz rubber cloth fiber board and production process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2749277C1 (en) * | 2019-12-25 | 2021-06-07 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Method of production of polishing polymer compositions for painting cans |
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| CN108586686A (en) * | 2018-04-20 | 2018-09-28 | 中国林业科学研究院林产化学工业研究所 | Epoxy anacardol/amino silicone modified synergic phenolic resin and its preparation method and application |
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| CN115785612A (en) * | 2022-12-14 | 2023-03-14 | 广西北海翰鑫木业科技有限公司 | Quartz rubber cloth fiber board and production process thereof |
| CN115785612B (en) * | 2022-12-14 | 2023-06-27 | 广西北海翰鑫木业科技有限公司 | Quartz rubber cloth fiber board and production process thereof |
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| CN106565923B (en) | 2018-10-30 |
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