CN106317766A - Preparation method of phenolic resin foam modified by cyanate ester resin - Google Patents
Preparation method of phenolic resin foam modified by cyanate ester resin Download PDFInfo
- Publication number
- CN106317766A CN106317766A CN201610809906.7A CN201610809906A CN106317766A CN 106317766 A CN106317766 A CN 106317766A CN 201610809906 A CN201610809906 A CN 201610809906A CN 106317766 A CN106317766 A CN 106317766A
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- China
- Prior art keywords
- phenolic resin
- ester group
- acid ester
- cyanic acid
- preparation
- Prior art date
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 70
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 70
- 239000006260 foam Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920005989 resin Polymers 0.000 title claims abstract description 28
- 239000011347 resin Substances 0.000 title claims abstract description 28
- 239000004643 cyanate ester Substances 0.000 title abstract 4
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000005187 foaming Methods 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- -1 aldehyde compound Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 66
- 238000003756 stirring Methods 0.000 claims description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 125000004185 ester group Chemical group 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229920002866 paraformaldehyde Polymers 0.000 claims description 14
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 5
- 229920000053 polysorbate 80 Polymers 0.000 claims description 5
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000010257 thawing Methods 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 239000002736 nonionic surfactant Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004378 air conditioning Methods 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract description 2
- 229920001169 thermoplastic Polymers 0.000 abstract description 2
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 abstract 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2461/14—Modified phenol-aldehyde condensates
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a resin foam preparation method, in particular to a preparation method of phenolic resin foam modified by cyanate ester resin. The phenolic resin foam modified by the cyanate ester resin comprises a phenolic compound, an aldehyde compound, a modifying agent, a catalyst, a surfactant and a foaming agent. The preparation method has the advantages that since cyanate-ester thermoplastic phenolic resin which is highly resistant to heat, low in water absorption rate and moisture content, capable of achieving an intrinsic toughening effect, beneficial to increase of percentage of close area and excellent in mechanical property is added into a foaming process of expandable phenolic resin by serving as the modifying agent, the modified phenolic resin foam is of low heat conductivity coefficient, high resistance to heat, high percentage of close area, high dimensional stability and excellent mechanical properties and can be widely applied to the fields of heat insulation and heat preservation of buildings, internal and external fireproof wallboards, central air-conditioning air tube heat preservation materials and aerospace.
Description
Technical field
The present invention relates to a kind of resin foam preparation method, particularly relate to a kind of cyanic acid ester group resin modified phenolic aldehyde tree
Fat foam preparation processes.
Background technology
Phenolic foam is a kind of novel difficult combustion, low cigarette insulation material of preventing fires, it be by phenolic resin add fire retardant,
The closed pore rigid foam that smoke suppressant, foaming agent, firming agent and other auxiliary agent are made.Its most prominent feature is difficult combustion, low
Cigarette, high temperature resistance distortion.Phenolic foam starting materials abundance, cheap, and also production and processing is simple, and product purpose is extensive.But
Phenol formaldehyde foam toughness is poor, the percent opening of foam is higher, and these shortcomings limit its application.
Cyanic acid ester group phenolic resin is with linear phenol-aldehyde resin as skeleton, and phenolic hydroxyl group is substituted and shape by cyanate functional group
, there are three cyclizations in the formaldehyde-phenol resin derivative become under heat and catalyst action, generates the height crosslinking containing triazine ring close
Degree network structure macromole.Its curing reaction is self-curing system, during solidification the little molecule of non-volatility produce, shrinkage factor low.Tool
There are excellent thermostability, prominent heat and thermo oxidative stability, and there is good mechanical property.
Chinese patent CN 105601856A discloses the preparation method of a kind of isocyanate-modified phenolic resin foam, should
Invention introduces isocyanates during Foaming of phenolic resin, is generated with isocyanates generation chemical reaction by phenolic resin
A kind of flame retarding construction, compared with tradition phenolic resin foam, fire resistance is greatly improved.But this invented technology difficulty is higher, instead
Difficulty should control, and the product strength prepared is relatively low.Chinese patent CN 103724931A discloses a kind of cyanic acid ester group phenolic aldehyde
Resin and span propargyl phenolic resin composite, this invention is Novolac Cyanate Eater Resin and span propargyl phenolic resin to be existed
Stir under uniform temperature, obtain resin prepreg material, then coated with in quartz fiber cloth, solidify, the phenol of gained
Urea formaldehyde material rate of closed hole is high, the most still can have preferable mechanical property.Chinese patent CN 104327451A is public
Having opened a kind of Aromatic Polyester Polyols as toughening agent modified phenol formaldehyde foam and preparation method thereof, this invention is at Foaming of phenolic resin
During add Aromatic Polyester Polyols and improve significantly as intrinsic toughening agent phenol-formaldehyde resin modified, phenol formaldehyde foam toughness,
Comprehensive mechanical property is good, and expansion rate is easy to control, but heat conductivity is higher, limits its range of application, the most involved
In patent field, the most not phenolic resin modified to cyanic acid ester group phenol formaldehyde foam is probed into, based on cyanic acid ester group phenolic resin
Various superior functions, the present invention relates to the phenolic resin modified expandable phenolic resin foam of a kind of cyanic acid ester group and preparation side
Method.
Summary of the invention
It is an object of the invention to provide a kind of cyanic acid ester group resin modified phenolic resin foam preparation method, the present invention
By the method mixing solidification, during tradition Foaming of phenolic resin, addition cyanic acid ester group phenolic resin is as modifying agent,
To a kind of phenolic resin foam composite, improve the spies such as tradition phenolic resin percent opening height, poor toughness, efflorescence degree be low
Point.
It is an object of the invention to be achieved through the following technical solutions:
A kind of cyanic acid ester group resin modified phenolic resin foam preparation method, is prepared by following method:
(1) preparation method of expandable phenolic resin:
(1-1) get the raw materials ready by following components and weight portion content: phenol 100, paraformaldehyde 40-60, catalyst A1, PH regulator,
(1-2) bath temperature is arranged on 60 DEG C, the phenol of thawing is joined equipped with thermometer and magnetic rotor by proportioning
In there-necked flask, add the 1% of catalyst A(phenol addition) stir, about 5min, make phenol be activated, more in batches
Add paraformaldehyde, add in controlling half an hour, be incubated half an hour after all adding and make paraformaldehyde fully react；Fully reaction
After gradually rise temperature to 90 DEG C, isothermal reaction about an and a half hours, use PH regulator regulation PH to 7-8, by synthetic
Phenolic resin cooling 24h can obtain basic expandable phenolic resin；
(2) cyanic acid ester group phenolic resin and the mixed foaming of expandable phenolic resin:
(2-1) get the raw materials ready by following components and weight portion content: expandable phenolic resin 100, cyanic acid ester group phenolic resin 10-40,
Catalyst B4-12, foaming agent 5-10, surfactant 8-10；
(2-2) expandable phenolic resin is added surfactant, foaming agent quickly stirs, then adds cyanic acid ester group phenolic aldehyde tree
The fat uniform stirring 20-30 second, the rear catalyst B that adds carries out continuing to stir；Pour mould into and put in 70 DEG C of baking ovens the most very
Take out after clock, obtain the phenol formaldehyde foam that cyanic acid ester group is phenolic resin modified.
Described cyanic acid ester group resin modified phenolic resin foam preparation method, used catalyst A is sodium hydroxide.
Described cyanic acid ester group resin modified phenolic resin foam preparation method, PH regulator used is acetic acid.
Described cyanic acid ester group resin modified phenolic resin foam preparation method, used catalyst B is organic acid, logical
It is often the one in oxalic acid, adipic acid, toluenesulfonic acid, benzenesulfonic acid, preferably benzenesulfonic acid or toluenesulfonic acid.
Described cyanic acid ester group resin modified phenolic resin foam preparation method, foaming agent used is pentane or isoamyl
One or more in alkane.
Described cyanic acid ester group resin modified phenolic resin foam preparation method, surfactant used is nonionic
The one of surfactant, preferably tween 80 or span.
Described cyanic acid ester group resin modified phenolic resin foam preparation method, cyanic acid ester group phenolic resin used is city
Sell the one in model PT-15 or PT-30.
Advantages of the present invention with effect is:
The present invention is added in foaming process at expandable phenolic resin as modifying agent by cyanate based thermoplastic phenolic resin,
Therefore fine heat-resisting performance, water absorption rate is low, self has intrinsic toughening effect, and moisture content is low, is conducive to improving rate of closed hole, and has
Excellent mechanical property, has through modified phenolic resin foam that heat conductivity is low, heat-resist, rate of closed hole is high, size is steady
The features such as qualitative good and good mechanical performance.Can be widely applied to building insulation, be incubated, inside and outside wall board of preventing fires, central air-conditioning
The fields such as pipe insulation material and Aero-Space.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
Below in conjunction with being embodied as example, the present invention will be further described, not limiting of its scope.Simultaneously
Experimental technique described in following embodiment, if no special instructions, is conventional method；Described reagent and material, as without special
Illustrate, the most commercially obtain.
Embodiment 1
The present invention is a kind of resin modified phenolic resin foam of cyanic acid ester group and preparation method, comprises the following steps:
(1) bath temperature is arranged on about 60 DEG C, 100 parts of phenol are joined three mouthfuls of burnings equipped with thermometer and magnetic rotor
In Ping, add 1 part of sodium hydroxide and stir, about 5min, make phenol be activated, then add 40 parts of paraformaldehydes in batches,
Add in controlling half an hour, be incubated half an hour after all adding and make paraformaldehyde fully react.Fully gradually rise temperature after reaction
Degree is to 90 DEG C, and isothermal reaction about an and a half hours, use acetic acid regulation PH to 7-8, synthetic phenolic resin is cooled down 24h can
Obtain basic expandable phenolic resin.
(2) in 100 parts of expandable phenolic resins obtained above, span 10 parts, 8 parts of quick stirrings of pentane are added equal
Even, add 20 parts of cyanic acid ester group phenolic resin uniform stirring 20-30 seconds, 8 parts of benzenesulfonic acids of rear addition carry out continuing to stir.
Pour mould into and put into taking-up after about ten minutes in 70 DEG C of baking ovens, obtain the phenol formaldehyde foam that cyanic acid ester group is phenolic resin modified.
Embodiment 2
The present invention is a kind of resin modified phenolic resin foam of cyanic acid ester group and preparation method, comprises the following steps:
(1) bath temperature is arranged on about 60 DEG C, 100 parts of phenol are joined three mouthfuls of burnings equipped with thermometer and magnetic rotor
In Ping, add 1 part of sodium hydroxide and stir, about 5min, make phenol be activated, then add 50 parts of paraformaldehydes in batches,
Add in controlling half an hour, be incubated half an hour after all adding and make paraformaldehyde fully react.Fully gradually rise temperature after reaction
Degree is to 90 DEG C, and isothermal reaction about an and a half hours, use acetic acid regulation PH to 7-8, synthetic phenolic resin is cooled down 24h can
Obtain basic expandable phenolic resin.
(2) add tween 80 8 parts in 100 parts of expandable phenolic resins obtained above, pentane 10 parts quickly stirs
Mixing uniformly, add 30 parts of cyanic acid ester group phenolic resin uniform stirring 40-50 seconds, 10 parts of toluenesulfonic acids of rear addition carry out continuing to stir
Mix uniformly.Pour mould into and put into taking-up after about ten minutes in 70 DEG C of baking ovens, obtain the phenolic aldehyde bubble that cyanic acid ester group is phenolic resin modified
Foam.
Embodiment 3
The present invention is a kind of resin modified phenolic resin foam of cyanic acid ester group and preparation method, comprises the following steps:
(1) bath temperature is arranged on about 60 DEG C, 100 parts of phenol are joined three mouthfuls of burnings equipped with thermometer and magnetic rotor
In Ping, add 1 part of sodium hydroxide and stir, about 5min, make phenol be activated, then add 45 parts of paraformaldehydes in batches,
Add in controlling half an hour, be incubated half an hour after all adding and make paraformaldehyde fully react.Fully gradually rise temperature after reaction
Degree is to 90 DEG C, and isothermal reaction about an and a half hours, use acetic acid regulation PH to 7-8, synthetic phenolic resin is cooled down 24h can
Obtain basic expandable phenolic resin.
(2) add tween 80 10 parts in 100 parts of expandable phenolic resins obtained above, pentane 88 parts quickly stirs
Mixing uniformly, add 40 parts of cyanic acid ester group phenolic resin uniform stirring 20-30 seconds, rear 10 parts of benzenesulfonic acids of addition carry out continuing stirring
Uniformly.Pour mould into and put into taking-up after about ten minutes in 70 DEG C of baking ovens, obtain the phenol formaldehyde foam that cyanic acid ester group is phenolic resin modified.
Embodiment 4
The present invention is a kind of resin modified phenolic resin foam of cyanic acid ester group and preparation method, comprises the following steps:
(1) bath temperature is arranged on about 60 DEG C, 100 parts of phenol are joined three mouthfuls of burnings equipped with thermometer and magnetic rotor
In Ping, add 1 part of sodium hydroxide and stir, about 5min, make phenol be activated, then add 55 parts of paraformaldehydes in batches,
Add in controlling half an hour, be incubated half an hour after all adding and make paraformaldehyde fully react.Fully gradually rise temperature after reaction
Degree is to 90 DEG C, and isothermal reaction about an and a half hours, use acetic acid regulation PH to 7-8, synthetic phenolic resin is cooled down 24h can
Obtain basic expandable phenolic resin.
(2) add tween 80 10 parts in 100 parts of expandable phenolic resins, isopentane 8 parts quickly stirs, then adds
Entering 40 parts of cyanic acid ester group phenolic resin uniform stirring 20-30 seconds, 30 parts of toluenesulfonic acids of rear addition carry out continuing to stir.Pour into
Mould is put in 70 DEG C of baking ovens and is taken out after about ten minutes, obtains the phenol formaldehyde foam that cyanic acid ester group is phenolic resin modified.
Following table is the Performance comparision of each embodiment and tradition phenol formaldehyde foam:
The phenolic resin foam that the present invention is produced, improves during traditional Foaming of phenolic resin, is prepared for cyanic acid
The phenolic resin foam that ester group is phenolic resin modified, owing to cyanic acid self water absorption rate of ester group phenolic resin is low, itself has interior increasing
Moulding effect, on the other hand moisture content is low, is conducive to improving rate of closed hole, and the addition of cyanic acid ester group phenolic resin makes system thermostability good
Good, good through testing whole Miscibility, it is easy to industrialization, to apply quite varied, whole technical process is released without toxic solvent
Put, be the environmental friendliness shaped material of a kind of nontoxic pollution-free.
Claims (7)
1. a cyanic acid ester group resin modified phenolic resin foam preparation method, it is characterised in that prepared by following method:
The preparation method of expandable phenolic resin:
(1-1) get the raw materials ready by following components and weight portion content: phenol 100, paraformaldehyde 40-60, catalyst A1, PH regulator,
(1-2) bath temperature is arranged on 60 DEG C, the phenol of thawing is joined equipped with thermometer and magnetic rotor by proportioning
In there-necked flask, add the 1% of catalyst A(phenol addition) stir, about 5min, make phenol be activated, more in batches
Add paraformaldehyde, add in controlling half an hour, be incubated half an hour after all adding and make paraformaldehyde fully react；Fully reaction
After gradually rise temperature to 90 DEG C, isothermal reaction about an and a half hours, use PH regulator regulation PH to 7-8, by synthetic
Phenolic resin cooling 24h can obtain basic expandable phenolic resin；
Cyanic acid ester group phenolic resin and the mixed foaming of expandable phenolic resin:
(2-1) get the raw materials ready by following components and weight portion content: expandable phenolic resin 100, cyanic acid ester group phenolic resin 10-40,
Catalyst B4-12, foaming agent 5-10, surfactant 8-10；
(2-2) expandable phenolic resin is added surfactant, foaming agent quickly stirs, then adds cyanic acid ester group phenolic aldehyde tree
The fat uniform stirring 20-30 second, the rear catalyst B that adds carries out continuing to stir；Pour mould into and put in 70 DEG C of baking ovens the most very
Take out after clock, obtain the phenol formaldehyde foam that cyanic acid ester group is phenolic resin modified.
Cyanic acid ester group the most according to claim 1 resin modified phenolic resin foam preparation method, it is characterised in that institute
It is sodium hydroxide with catalyst A.
Cyanic acid ester group the most according to claim 1 resin modified phenolic resin foam preparation method, it is characterised in that institute
It is acetic acid with PH regulator.
Cyanic acid ester group the most according to claim 1 resin modified phenolic resin foam preparation method, it is characterised in that institute
Be organic acid with catalyst B, the usually one in oxalic acid, adipic acid, toluenesulfonic acid, benzenesulfonic acid, preferably benzenesulfonic acid or
Toluenesulfonic acid.
Cyanic acid ester group the most according to claim 1 resin modified phenolic resin foam preparation method, it is characterised in that institute
It is one or more in pentane or isopentane with foaming agent.
Cyanic acid ester group the most according to claim 1 resin modified phenolic resin foam preparation method, it is characterised in that institute
By the one that surfactant is nonionic surfactant, preferably tween 80 or span.
Cyanic acid ester group the most according to claim 1 resin modified phenolic resin foam preparation method, it is characterised in that institute
It is the one in commercially available model PT-15 or PT-30 with cyanic acid ester group phenolic resin.
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Application publication date: 20170111 Assignee: SHENYANG XINFEIYU RUBBER PRODUCTS CO.,LTD. Assignor: SHENYANG University OF CHEMICAL TECHNOLOGY Contract record no.: X2023210000283 Denomination of invention: A preparation method of phenolic resin foam modified by cyanate ester resin Granted publication date: 20180515 License type: Common License Record date: 20231205 |