CN106397703B - A kind of aralkyl ethers modified pnenolic aldehyde foam material - Google Patents
A kind of aralkyl ethers modified pnenolic aldehyde foam material Download PDFInfo
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- CN106397703B CN106397703B CN201610809907.1A CN201610809907A CN106397703B CN 106397703 B CN106397703 B CN 106397703B CN 201610809907 A CN201610809907 A CN 201610809907A CN 106397703 B CN106397703 B CN 106397703B
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- aralkyl
- phenol
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- aralkyl ethers
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- -1 aralkyl ethers Chemical class 0.000 title claims abstract description 39
- 239000006261 foam material Substances 0.000 title claims abstract description 19
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 56
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 44
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 26
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005011 phenolic resin Substances 0.000 claims abstract description 21
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims abstract description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000002989 phenols Chemical class 0.000 claims abstract description 7
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 5
- 150000002170 ethers Chemical class 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 150000001299 aldehydes Chemical class 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims 1
- 229920001807 Urea-formaldehyde Polymers 0.000 claims 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims 1
- 229940092714 benzenesulfonic acid Drugs 0.000 claims 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000006260 foam Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 102000004895 Lipoproteins Human genes 0.000 description 5
- 108090001030 Lipoproteins Proteins 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000012661 block copolymerization Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HXMUYYHTXVEPPM-UHFFFAOYSA-N [S].CC1=C(C=CC=C1)C Chemical compound [S].CC1=C(C=CC=C1)C HXMUYYHTXVEPPM-UHFFFAOYSA-N 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- BKUYVGOACRJHQO-UHFFFAOYSA-N benzenesulfonic acid;sulfuric acid Chemical compound OS(O)(=O)=O.OS(=O)(=O)C1=CC=CC=C1 BKUYVGOACRJHQO-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
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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
- C08G8/36—Chemically modified polycondensates by etherifying
-
- 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
- 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
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
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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
-
- 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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- 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
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- 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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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
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- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
A kind of aralkyl ethers modified pnenolic aldehyde foam material, is related to a kind of foamed material, and the process that the material produces aralkyl ethers phenol-formaldehyde resin modified is divided into following two stages of reaction；Stage of reaction I is that exchange reaction occurs for methoxyl aralkyl ether oligomers and phenol, generates the aralkyl ethers compound of two phenol rings of band；Stage of reaction II is to be reacted under alkaline condition using stage of reaction I aralkyl ethers compound generated with formaldehyde, generates modified phenolic resin；The present invention is reacted after modified phenol with formaldehyde with methoxyl aralkyl ether oligomers, i.e., aryl or aralkyl is introduced on phenol ring, reacts with formaldehyde generate a kind of novel expandable phenolic resin under alkaline condition.This new type resin mechanical strength is higher, and Residual carbon, thermal decomposition peak temperature and hardness are improved, and the comprehensive performance of product is improved.In addition, its manufacturing process is simple, there is wide development and application prospect.
Description
Technical field
The present invention relates to a kind of foamed materials, more particularly to a kind of aralkyl ethers modified pnenolic aldehyde foam material.
Background technique
In the current wall heat insulation material market of China, phenol formaldehyde foam is because of its low heat conductivity, outstanding fire resistance
Can, low water absorbable and in burning less toxic cigarette generation rate, and enter in the eye of people, be known as " king of thermal insulation material ".By
There is benzene ring structure in phenolic aldehyde, so phenol formaldehyde foam dimensionally stable, and chemical composition stability, be usually used in being suitable for building, chemical industry,
Ship and various utilidors.But phenol formaldehyde foam also has a disadvantage, for example matter brittleness, easily loses powder scaling-off, density is to the strong of foam
Degree, thermal coefficient are affected, these disadvantages constrain phenol formaldehyde foam in the application of every field significantly.
Phenol formaldehyde foam usually adds curing agent by resol, surfactant, foaming agent after mixing, stirs
The defects of foamable after mixing uniformly is formed by phenol formaldehyde foam and there is density height under normal circumstances, and brittleness is big, and water absorption rate is high,
So the phenolic resin that phenolic foam foaming uses needs that flexible material is used to be modified, lacked to solve the part of phenol formaldehyde foam
It falls into.The flexible material of modified phenolic foam generally comprises: polyethylene glycol, low molecular weight polyester, additional toughener etc..By modification
Phenolic resin carry out the phenol formaldehyde foam of foaming preparation, brittleness can have some improvement.And the method for external plasticization is used, plasticising
It is ineffective, therefore the defect of its poor toughness need to be overcome, it also needs to solve using intrinsic toughening method.
Most researchers replace phenol using anacardol or the toughener such as urea, lignin are added to solve at this stage
The poor problem of phenolic resin toughness, but during phenolic resin composite obtained the dispersion of lignin be difficult to uniformly,
Required solidification temperature is excessively high in foaming process, and curing rate is excessively slow.That there are abscesses is uneven for phenol formaldehyde foam, and cracking etc. easily occurs and lacks
Point.
Publication number is the application for a patent for invention of 101186564 A of CN, and it discloses a kind of methoxyl aralkyl ether is low
The technology of preparing of polymers can be used for a variety of phenol-formaldehyde resin modifieds.Which describe the preparation of this methoxyl aralkyl ether oligomers,
It is not expressly recited and how to apply in the modification of thermosetting phenolic resin and modified have what benefit to phenolic resin.
Summary of the invention
The purpose of the present invention is to provide a kind of aralkyl ethers modified pnenolic aldehyde foam material, methoxyl aralkyl ethers of the present invention
It is reacted after oligomer modified phenol with formaldehyde, generates a kind of side of novel thermosetting modification phenolic resin under alkaline condition
Method.The phosphorus content of phenolic resin is mainly improved, and the bond energy of aromatic ring is higher, stable structure, therefore obtained phenol formaldehyde foam is tough
The comprehensive performances such as the water absorption rate that property greatly improves, while improving phenol formaldehyde foam.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of aralkyl ethers modified pnenolic aldehyde foam material, the material produce the process point of aralkyl ethers phenol-formaldehyde resin modified
For following two stages of reaction；Stage of reaction I is that exchange reaction occurs for methoxyl aralkyl ether oligomers and phenol, generates band two
The aralkyl ethers compound of a phenol ring；Stage of reaction II is to use stage of reaction I aralkyl ethers compound generated and formaldehyde
It reacts under alkaline condition, generates modified phenolic resin；
；
。
A kind of aralkyl ethers modified pnenolic aldehyde foam material is prepared by the raw material of following parts by weight:
70-85 parts of methoxyl aralkyl ether oligomers；
80-100 parts of phenol；
46-56 parts of paraformaldehyde；
1 part of sodium hydroxide.
A kind of aralkyl ethers modified pnenolic aldehyde foam material, raw material and proportion it is selected after, by following preparation process into
Row:
To take obtained methoxyl aralkyl ether oligomers and phenol according to aforementioned proportion fully reacting after, be added above-mentioned
The formalin and sodium hydroxide catalyst of ratio, after reacting 2 hours at 80~100 DEG C, vacuum dehydration；When resin gel
Between stop reaction when reaching 120~175 s, the sticky solid resin of yellow can be obtained.
A kind of aralkyl ethers modified pnenolic aldehyde foam material, the aralkyl ether oligomers of selected modified phenol are
Methoxyl aralkyl ether oligomers, added aralkyl compound is toluene, diphenyl ether, paraxylene etc. in reaction process
Compound aromatic base.
The aralkyl ethers modified pnenolic aldehyde foam material is prepared by the raw material of following parts by weight:
100 parts of phenolic resin；
2-6 parts of surfactant；
8-10 parts of foaming agent；
12-14 parts of curing agent.
A kind of aralkyl ethers modified pnenolic aldehyde foam material, surfactant are polysiloxanes-polyoxyethylene-polyoxy
At least one of the block copolymer of propylene, Tween-80, silicone oil.
A kind of aralkyl ethers modified pnenolic aldehyde foam material, the foaming agent are methylene chloride, pentane, isopentane
At least one of.
A kind of aralkyl ethers modified pnenolic aldehyde foam material, the curing agent are p-methyl benzenesulfonic acid, dimethylbenzene sulphur
One of one or more of acid, phenolsulfonic acid, benzene sulfonic acid sulfuric acid is a variety of.
The advantages and effects of the present invention are:
The present invention reacts after having selected a kind of methoxyl aralkyl ether oligomers to carry out modified phenol with formaldehyde, i.e., on phenol ring
Aryl or aralkyl is introduced, is reacted with formaldehyde generate a kind of novel expandable phenolic resin under alkaline condition.It is this novel
Resin mechanical strength is higher, and Residual carbon, thermal decomposition peak temperature and hardness are improved, and the comprehensive performance of product is mentioned
It rises.In addition, its manufacturing process is simple, there is wide development and application prospect.
Specific embodiment
The following describes the present invention in detail with reference to examples.
Embodiment 1
The concentrated sulfuric acid is added into formalin according to the molar ratio of 2:1, is added two according to the molar ratio of 1:3 after room temperature
Phenylate and methanol are uniformly mixed, and are put into three-necked flask, and 65 DEG C after water-bath 1 hour, agitating and heating heats up water-bath to 80 DEG C, reaction
It is cooled to room temperature after 6 hours and takes upper liquid, removed excessive moisture and obtain required methoxyl aralkyl ether oligomers.It will be acquired
Methoxyl aralkyl ether oligomers and phenol according to the portion rate of 70:100 be added to tri- mouthfuls of the 500ml with reflux condensing tube
In flask, stirring is warming up to 110 DEG C, fully reacting after two hours；56 parts of formalins and 1 are added after being cooled to 100 DEG C in room temperature
Part sodium hydroxide catalyst, after reacting 2 hours at 80~100 DEG C, vacuum dehydration；Reach 120~175 when the resin gel time
Stop reaction when s, the sticky solid resin of yellow can be obtained.Ethanol solution is added after sampling and is stirred dissolution, is changed
Property phenol resin solution, by the block copolymerization of resulting modified phenolic resin lipoprotein solution and polysiloxane-polyoxyethylene-poly-oxypropylene
Object, methylene chloride carry out full and uniform mixing according to the portion rate of 100:2:8, stir 3 minutes, then by 12 parts of p-methyl benzenesulfonic acids
Be added stirring 15 seconds, then the material mixed is transferred in mold, reacted under 70 DEG C of baking ovens demoulded after ten minutes,
The phenol formaldehyde foam of needs can be obtained in demoulding.
Embodiment 2
The concentrated sulfuric acid is added into formalin according to the molar ratio of 2:1, according to the molar ratio addition pair of 1:3 after room temperature
Dimethylbenzene and methanol are uniformly mixed, and are put into three-necked flask, and 65 DEG C after water-bath 1 hour, agitating and heating heats up water-bath to 80 DEG C, instead
It is cooled to room temperature after answering 6 hours and takes upper liquid, removed excessive moisture and obtain required methoxyl aralkyl ether oligomers.It will be taken
The methoxyl aralkyl ether oligomers and phenol obtained are added to the 500ml tri- with reflux condensing tube according to the portion rate of 75:95
In mouth flask, stirring is warming up to 110 DEG C, fully reacting after two hours；Room temperature be added after being cooled to 100 DEG C 52 parts of formalins and
1 part of sodium hydroxide catalyst, after reacting 2 hours at 80~100 DEG C, vacuum dehydration；When the resin gel time reaches 120~
Stop reaction when 175 s, the sticky solid resin of yellow can be obtained.Ethanol solution is added after sampling and is stirred dissolution, obtains
To modified phenolic resin lipoprotein solution, by the block of resulting modified phenolic resin lipoprotein solution and polysiloxane-polyoxyethylene-poly-oxypropylene
Copolymer, methylene chloride carry out full and uniform mixing according to the portion rate of 100:3:8, stir 3 minutes, then by 12 parts to methylbenzene
Stirring 15 seconds is added in sulfonic acid, and then the material mixed is transferred in mold, reacts under 70 DEG C of baking ovens and carries out after ten minutes
Demoulding, demoulding, can be obtained the phenol formaldehyde foam of needs.
Embodiment 3
The concentrated sulfuric acid is added into formalin according to the molar ratio of 2:1, first is added according to the molar ratio of 1:3 after room temperature
Benzene and methanol are uniformly mixed, and are put into three-necked flask, and 65 DEG C after water-bath 1 hour, agitating and heating heats up water-bath to 80 DEG C, reaction 6
It is cooled to room temperature after hour and takes upper liquid, removed excessive moisture and obtain required methoxyl aralkyl ether oligomers.It will be acquired
Methoxyl aralkyl ether oligomers and phenol according to the portion rate of 80:90 be added to tri- mouthfuls of the 500ml with reflux condensing tube
In flask, stirring is warming up to 110 DEG C, fully reacting after two hours；49 parts of formalins and 1 are added after being cooled to 100 DEG C in room temperature
Part sodium hydroxide catalyst, after reacting 2 hours at 80~100 DEG C, vacuum dehydration；Reach 120~175 when the resin gel time
Stop reaction when s, the sticky solid resin of yellow can be obtained.Ethanol solution is added after sampling and is stirred dissolution, is changed
Property phenol resin solution, by the block copolymerization of resulting modified phenolic resin lipoprotein solution and polysiloxane-polyoxyethylene-poly-oxypropylene
Object, methylene chloride carry out full and uniform mixing according to the portion rate of 100:4:8, stir 3 minutes, then by 13 parts of p-methyl benzenesulfonic acids
Be added stirring 15 seconds, then the material mixed is transferred in mold, reacted under 70 DEG C of baking ovens demoulded after ten minutes,
The phenol formaldehyde foam of needs can be obtained in demoulding.
Embodiment 4
The concentrated sulfuric acid is added into formalin according to the molar ratio of 2:1, is added two according to the molar ratio of 1:3 after room temperature
Phenylate and methanol are uniformly mixed, and are put into three-necked flask, and 65 DEG C after water-bath 1 hour, agitating and heating heats up water-bath to 80 DEG C, reaction
It is cooled to room temperature after 6 hours and takes upper liquid, removed excessive moisture and obtain required methoxyl aralkyl ether oligomers.It will be acquired
Methoxyl aralkyl ether oligomers and phenol according to the portion rate of 85:80 be added to tri- mouthfuls of the 500ml with reflux condensing tube
In flask, stirring is warming up to 110 DEG C, fully reacting after two hours；52 parts of formalins and 1 are added after being cooled to 100 DEG C in room temperature
Part sodium hydroxide catalyst, after reacting 2 hours at 80~100 DEG C, vacuum dehydration；Reach 120~175 when the resin gel time
Stop reaction when s, the sticky solid resin of yellow can be obtained.Ethanol solution is added after sampling and is stirred dissolution, is changed
Property phenol resin solution, by the block copolymerization of resulting modified phenolic resin lipoprotein solution and polysiloxane-polyoxyethylene-poly-oxypropylene
Object, methylene chloride carry out full and uniform mixing according to the portion rate of 100:4:9, stir 3 minutes, then by 13 parts of p-methyl benzenesulfonic acids
Be added stirring 15 seconds, then the material mixed is transferred in mold, reacted under 70 DEG C of baking ovens demoulded after ten minutes,
The phenol formaldehyde foam of needs can be obtained in demoulding.
The performance comparison of phenol formaldehyde foam prepared by the embodiment of the present invention 1 to 4 and common phenol formaldehyde foam is as follows:
As seen from the above table, with the increase of phenyl ring content in phenol-formaldehyde resin modified, the Bending Deformation degree of foam is also therewith
Increase, the Bending Deformation of foam improves 4~5 times than base foam.This is because introducing structure in phenolic resin more
Stable aryl, improves the toughness of material, while increasing the length of strand, increases the steric hindrance of system, reduces
The network compactness of phenolic resin, keeps phenolic resin not easy to break.The increase of phenyl ring changes only sub- between phenolic resin
The connected situation of methyl, therefore in phenolic resin introduce phenyl ring and carry out phenol-formaldehyde resin modified and can improve crisp, the easy dusting of foam matter
Disadvantage improves the toughness of material.
With the increase of carbon content in phenol-formaldehyde resin modified, the modified phenol formaldehyde foam of methoxyl aralkyl ether and common
The carbon yield result of phenol formaldehyde foam relatively can be seen that, promote higher carbon content, so that modified phenol formaldehyde foam is than general
Logical phenol formaldehyde foam carbon yield improves about 10 percentage points.The reason is that phenyl ring class methyl-derivatives, phenols and its methyl are derivative
The volatile quantity of object etc. is all reduced, and the carbon yield of resin is substantially increased.
With the increase of phenyl ring content, modified phenolic foam thermal decomposition peak temperature is up to 513.4 DEG C, more common phenolic aldehyde
Foam improves nearly 100 DEG C, and resistance to stability significantly improves.
According to requirements of the national standard GB8624-2012 construction material be classified require, the above invention meet National Fire every
Hot standard, after adding phenyl ring content increase, its hardness of embodiment 1-4 improves one etc. than the hardness of common phenol formaldehyde foam
Grade.
In conclusion the phenolic resin that the present invention is generated by aralkyl ether oligomers modified phenol and formaldehyde, steeps phenolic aldehyde
Foam toughness substantially improves, and carbon yield, thermal decomposition peak temperature, hardness are improved, and the comprehensive performance of product is improved.On
That states example use produces the aralkyl compound being added in the method for aralkyl ether oligomers, is equally applicable to other same point
Isomers.
Above by the description of specific embodiment, the invention will be further described, but it is to limit of the invention that this, which is not,
System, those skilled in the art's basic thought according to the present invention can make various modifications or improvements, but without departing from this
The basic thought of invention, is all within the scope of the present invention.
Claims (6)
1. a kind of aralkyl ethers modified pnenolic aldehyde foam material, which is characterized in that prepared by the raw material of following parts by weight:
100 parts of aralkyl ethers phenol-formaldehyde resin modified；
2-6 parts of surfactant；
8-10 parts of foaming agent；
12-14 parts of curing agent；
The process that the aralkyl ethers phenol-formaldehyde resin modified is produced is divided into following two stages of reaction；Stage of reaction I is methoxyl group
Exchange reaction occurs for aralkyl ether oligomers and phenol, generates the aralkyl ethers compound of two phenol rings of band；Stage of reaction II is
It is reacted under alkaline condition using stage of reaction I aralkyl ethers compound generated with formaldehyde, generates the modified phenol of aralkyl ethers
Urea formaldehyde；
；
。
2. a kind of aralkyl ethers modified pnenolic aldehyde foam material as described in claim 1, which is characterized in that the aralkyl ethers changes
Property phenolic resin by following parts by weight raw material prepare:
70-85 parts of methoxyl aralkyl ether oligomers；
80-100 parts of phenol；
46-56 parts of paraformaldehyde；
1 part of sodium hydroxide.
3. a kind of aralkyl ethers modified pnenolic aldehyde foam material as claimed in claim 2, which is characterized in that the aralkyl ethers
After modified phenolic resin fat raw material and proportion are selected, carried out by following preparation process:
To take obtained methoxyl aralkyl ether oligomers and phenol according to aforementioned proportion fully reacting after, aforementioned proportion is added
Formalin and sodium hydroxide catalyst, after reacting 2 hours at 80~100 DEG C, vacuum dehydration；It is reached when the resin gel time
Stop reaction when to 120~175 s, the sticky solid resin of yellow can be obtained.
4. a kind of aralkyl ethers modified pnenolic aldehyde foam material as described in claim 1, which is characterized in that surfactant is poly-
At least one of polysiloxane-polyoxy ethylene-polyoxypropylene block copolymer, Tween-80, silicone oil.
5. a kind of aralkyl ethers modified pnenolic aldehyde foam material as described in claim 1, which is characterized in that the foaming agent is two
At least one of chloromethanes, pentane, isopentane.
6. a kind of aralkyl ethers modified pnenolic aldehyde foam material as described in claim 1, which is characterized in that the curing agent is pair
One or more of toluenesulfonic acid, xylene monosulfonic acid, phenolsulfonic acid, benzene sulfonic acid.
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| US3579470A (en) * | 1968-12-30 | 1971-05-18 | Westinghouse Electric Corp | Diphenyl oxide modified phenolic resin insulating varnishes |
| JPS5075295A (en) * | 1973-11-07 | 1975-06-20 | ||
| CN1803887A (en) * | 2005-12-31 | 2006-07-19 | 四川东材企业集团有限公司 | Benzoxazine resin containing aralkyl structure, its preparation method and use |
| CN101186564B (en) * | 2007-11-09 | 2011-06-15 | 华东理工大学 | Technique for preparing methoxyl aralkyl ether oligomers |
| CN101265165A (en) * | 2008-04-29 | 2008-09-17 | 华东理工大学 | Aralkyl ether oligomer containing hydroxy benzene and preparation method thereof |
| CN102994043A (en) * | 2012-10-18 | 2013-03-27 | 殷国忠 | Modified phenolic resin-based friction material |
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