CN102336878A - Low free phenol phenolic resin and preparation method thereof - Google Patents
Low free phenol phenolic resin and preparation method thereof Download PDFInfo
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- CN102336878A CN102336878A CN2011102002099A CN201110200209A CN102336878A CN 102336878 A CN102336878 A CN 102336878A CN 2011102002099 A CN2011102002099 A CN 2011102002099A CN 201110200209 A CN201110200209 A CN 201110200209A CN 102336878 A CN102336878 A CN 102336878A
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000005011 phenolic resin Substances 0.000 title abstract description 14
- 229920001568 phenolic resin Polymers 0.000 title abstract description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 172
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229920003987 resole Polymers 0.000 claims description 94
- 239000000463 material Substances 0.000 claims description 46
- 229920000642 polymer Polymers 0.000 claims description 30
- 239000003638 chemical reducing agent Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- -1 phenolic aldehyde Chemical class 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
- 125000005265 dialkylamine group Chemical group 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 125000005270 trialkylamine group Chemical group 0.000 claims description 6
- 229960001124 trientine Drugs 0.000 claims description 6
- 229960004418 trolamine Drugs 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 150000002429 hydrazines Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 238000006731 degradation reaction Methods 0.000 abstract 3
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 230000006837 decompression Effects 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 230000006378 damage Effects 0.000 description 7
- 238000010030 laminating Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000011175 product filtration Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000001627 detrimental effect Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000003822 preparative gas chromatography Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention provides a preparation method of a low free phenol phenolic resin, which comprises the following steps: a) phenol and aldehydes react under the condition of a basic catalyst at the temperature of 20-70 DEG C to obtain a phenolic prepolymer, wherein the mole ratio of the phenol to the aldehydes is 1: (3-5); and b) an aldehyde degradation agent is added into the phenolic prepolymer obtained in step a) to obtain the low free phenol phenolic resin after reaction. The invention also provides the low free phenol phenolic resin. In the phenolic resin, the content of free phenol is below 500ppm metered by phenol, and the content of free aldehydes is below 500ppm metered by formaldehyde. According to the invention, excessive aldehydes and phenol react at a low temperature, the phenol can react completely so as to reduce the content of free phenol in the phenolic resin prepolymer; and then the aldehyde degradation agent is added into the phenolic resin prepolymer, and the aldehyde degradation agent is reacted with the excessive aldehydes so as to reduce the content of the free aldehydes in the phenolic resin.
Description
Technical field
The invention belongs to the phenolic resins field, relate in particular to a kind of low free phenol resol and preparation method thereof.
Background technology
Resol is under the condition that catalyzer exists, the react general designation of the resin that generates of phenols and aldehydes; It is the macromolecular material of suitability for industrialized production the earliest; It has good dimensional stability, flame retardant properties, acid resistance, mechanical property and resistance toheat, is widely used in industry fields such as iron and steel, automobile, mechanical workout, electronic apparatus, aerospace.
Resol is raw material with phenol and formaldehyde generally; Because have phenol and formaldehyde residual in the resol that reaction is incomplete or other factors cause obtaining, wherein, phenol is highly toxic substance; Formaldehyde is I class carcinogenic substance; Be hazardous chemical, influence ecological environment not only, and be detrimental to health.In particular for producing the heat-reactive phenolic resin of dipping laminating material, when it was mixed with the solution of 70% following solid content, free phenol content was 5%～10% in the solution, and free formaldehyde content is about 1%.Because the production technique of dipping laminating material is with textile impregnation phenol resin solutions such as cotton, spun glass; Make solvent evaporates through baking oven for heating then; And then carry out heat pressing process and obtain laminating material; In drying course, free-phenol in the resol and free formaldehyde evaporate in the surrounding environment, influence ecological environment, are detrimental to health.
Prior art discloses the method for free aldehyde in the multiple removal resol; Like application number is that 200680044503.2 Chinese patent document discloses a kind of formaldehydeless phenolic resin adhesive compsn; The water dispersion, amine compound, activation silane and the aromatic hydroxy compound that comprise resol; This aromatic hydroxy compound can be caught the free formaldehyde in the resol water dispersion and it irreversibly is converted into the molecule of the crosslinking reaction that can not participate in resin; Thereby reduced the content of free formaldehyde in the resol water dispersion, alleviated formaldehyde the pollution of environment and the harm of HUMAN HEALTH.But, still contain a large amount of free-phenols in this resol water dispersion, still bigger to the harm of environment and HUMAN HEALTH.
Summary of the invention
In view of this, the technical problem that the present invention will solve is to provide a kind of low free phenol resol and preparation method thereof, and free phenol and content of free aldehyde are all lower in the resol provided by the invention, and is less to the harm of environment and HUMAN HEALTH.
The invention provides a kind of preparation method of low free phenol resol, may further comprise the steps:
A) phenol and aldehyde material react under 20 ℃～70 ℃, the condition of basic catalyst, obtain the phenolic aldehyde performed polymer, and the mol ratio of said phenol and aldehyde material is 1: (3～5);
B) in the phenolic aldehyde performed polymer that said step a) obtains, add formaldehyde reducing agent, obtain low free phenol resol after the reaction.
Preferably, in the said step a), said aldehyde material is one or more in formaldehyde, trioxymethylene and the Paraformaldehyde 96.
Preferably; In the said step a); Said basic catalyst is one or more in sodium hydroxide, Pottasium Hydroxide, hydrated barta, Marinco H and the calcium hydroxide, perhaps is in ammoniacal liquor, alkylamine, dialkylamine, trialkylamine, aniline, diethylenetriamine, triethylene tetramine, hexamethylenetetramine, diethylolamine and the trolamine one or more.
Preferably, in the said step a), the mol ratio of said basic catalyst and said phenol is (0.01～1): 1.
Preferably, in the said step a), the time of said reaction is 1h～24h.
Preferably, said step b) specifically comprises:
B1) in the phenolic aldehyde performed polymer that said step a) obtains, add formaldehyde reducing agent, reaction;
B2) to said step b1) add acid in the product that obtains and neutralize, obtain low free phenol resol.
Preferably; Said step b1) in; Said formaldehyde reducing agent is the verivate of ammoniacal liquor, Dyhard RU 100, trimeric cyanamide, an alkylamine, dialkylamine, trialkylamine, aniline, benzo guanamine, acetylguanamine, diethylenetriamine, triethylene tetramine, diethylolamine, trolamine, urea, urea, urea, one or more in Hydrazine Hydrate 80 and the hydrazine derivative.
Preferably, said step b2) in, said acid is one or more in phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetate, oxalic acid, Whitfield's ointment and the toluenesulphonic acids.
The present invention also provides a kind of low free phenol resol, and in the said resol, free phenol is below the 500ppm in phenol content, and free aldehyde is below the 500ppm in formaldehyde content.
Compared with prior art, the present invention is 1 with mol ratio at first: the phenol of (3～5) and aldehyde material are raw material, and reaction obtains the resol performed polymer under 20 ℃～70 ℃ low temperature environment; In said resol performed polymer, add formaldehyde reducing agent then, obtain all lower resol of free phenol and content of free aldehyde after the reaction.The present invention reacts with excessive aldehyde material and phenol at low temperatures, and phenol can react fully, thereby reduces the content of resol performed polymer middle reaches from phenol; In said resol performed polymer, add formaldehyde reducing agent then, formaldehyde reducing agent and excessive aldehyde material react, thereby reduce the content of free aldehyde in the resol.In the low free-phenol resol provided by the invention, the content of free phenol is counted below the 500ppm with phenol, and the content of free aldehyde is counted below the 500ppm with formaldehyde.Phenol in the resol provided by the invention and aldehyde material all take the method for chemical reaction to remove, and content is all lower, and be less to the harm of environment and HUMAN HEALTH.
Embodiment
The invention provides a kind of preparation method of low free phenol resol, may further comprise the steps:
A) phenol and aldehyde material react under 20 ℃～70 ℃, the condition of basic catalyst, obtain the phenolic aldehyde performed polymer, and the mol ratio of said phenol and aldehyde material is 1: (3～5);
B) in the phenolic aldehyde performed polymer that said step a) obtains, add formaldehyde reducing agent, obtain low free phenol resol after the reaction.
The present invention reacts with excessive aldehyde material and phenol at low temperatures, and phenol can react fully, thereby reduces the content of resol performed polymer middle reaches from phenol; In said resol performed polymer, add formaldehyde reducing agent then, formaldehyde reducing agent and excessive aldehyde material react, thereby reduce the content of free aldehyde in the resol.
At first phenol, aldehyde material and basic catalyst are mixed, be warming up to 20 ℃～70 ℃ and react, obtain the resol performed polymer, wherein, the mol ratio of phenol and aldehyde material is 1: (3～5).
The present invention is carrying out polycondensation with excessive aldehyde material and phenol under the effect of basic catalyst, under coldcondition, and phenol is complete reaction basically, thereby reduces the content of free phenol in the resol that obtains.
In the present invention, said aldehyde material is preferably one or more in formaldehyde, trioxymethylene and the Paraformaldehyde 96, more preferably formaldehyde.When said aldehyde material is formaldehyde, be raw material with the formalin preferably, the mass concentration of said formalin is preferably 15%～75%, and more preferably 20%～65%, most preferably be 37%～45%.
The mol ratio of said phenol and aldehyde material is 1: (3～5) are preferably 1: (3.5～5).In the present invention; The mol ratio of the aldehyde material of phenol is the key that obtains low free phenol and low-free formaldehyde resol, and when being lower than above-mentioned mol ratio, promptly the add-on of aldehyde material more after a little while; The reaction of phenol is incomplete, and free phenol content is higher in the resol that obtains; When being higher than above-mentioned mol ratio, promptly the add-on of aldehyde material more for a long time, though phenol reactant is complete, residual aldehyde material is more in the system, thus free aldehyde is higher in the resol that causes obtaining.
In the present invention; Said basic catalyst can be in sodium hydroxide, Pottasium Hydroxide, hydrated barta, Marinco H and the calcium hydroxide one or more; Also can be in ammoniacal liquor, alkylamine, dialkylamine, trialkylamine, aniline, diethylenetriamine, triethylene tetramine, hexamethylenetetramine, diethylolamine and the trolamine one or more; Be preferably sodium hydroxide, Pottasium Hydroxide or ammoniacal liquor, more preferably sodium hydroxide or Pottasium Hydroxide.The mol ratio of said basic catalyst and said phenol is preferably (0.01～1): 1, more preferably (0.02～0.5): 1.
The temperature that said phenol and aldehyde material carry out polycondensation is 20 ℃～70 ℃, is preferably 25 ℃～65 ℃; Time is preferably 1h～24h, more preferably 3h～20h.The temperature that phenol and aldehyde material carry out polycondensation is one of the key that obtains the resol of low-free formaldehyde and low free phenol, and when temperature was too high, phenol and aldehyde material reaction were too fast, are unfavorable for the abundant reaction of phenol and formaldehyde.
Mol ratio is 1: after the phenol of (3～5) and aldehyde material reaction finish, obtain the resol performed polymer, in the said resol performed polymer, the content of phenol is less than 500ppm.
After obtaining the resol performed polymer, in said resol performed polymer, add formaldehyde reducing agent, obtain resol after the reaction, specifically may further comprise the steps:
B1) in the phenolic aldehyde performed polymer that said step a) obtains, add formaldehyde reducing agent, reaction;
B2) to said step b1) add acid in the product that obtains and neutralize, obtain low free phenol resol.
Said formaldehyde reducing agent and excessive aldehyde material reaction generate the soluble small molecular material, thereby reduce the content of free aldehyde in the resol greatly.
According to the present invention; Said formaldehyde reducing agent is the formaldehyde reducing agent that can generate the soluble small molecular material with aldehyde material generation chemical reaction; Be preferably the verivate of ammoniacal liquor, Dyhard RU 100, trimeric cyanamide, an alkylamine, dialkylamine, trialkylamine, aniline, benzo guanamine, acetylguanamine, diethylenetriamine, triethylene tetramine, diethylolamine, trolamine, urea, urea, urea; In Hydrazine Hydrate 80 and the hydrazine derivative one or more; More preferably ammoniacal liquor, urea, Hydrazine Hydrate 80 or trimeric cyanamide most preferably are ammoniacal liquor, urea or Hydrazine Hydrate 80.
In the present invention, the mol ratio of said formaldehyde reducing agent and said phenol is preferably (3～10): 1, more preferably (3.5～8): 1.The temperature that said formaldehyde reducing agent and said aldehyde material react is preferably 20 ℃～50 ℃, and more preferably 25 ℃～45 ℃, the reaction times is restriction not, is preferably to react to the system aldehyde material and count below the 500ppm with formaldehyde.
After formaldehyde reducing agent and formolite reaction finish, neutralize, obtain low free phenol resol to wherein adding acid.
In the present invention; Said acid can be organic acid; Also can be mineral acid; Be preferably in phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetate, oxalic acid, Whitfield's ointment and the toluenesulphonic acids one or more, more preferably a kind of in phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid and the acetate the more plants, and most preferably is in phosphoric acid and the hydrochloric acid one or both.
With the product after the neutralization through filtration, wherein salt and small-molecule substance are removed in washing, obtain resol behind the decompression dehydration.The present invention has no restriction to said filtration, washing and decompression dehydration, those skilled in the art's resin, can realize that treatment step of the present invention gets final product.
The resol that preparation method provided by the invention obtains is heat-reactive phenolic resin; Vapor-phase chromatography according in YB/T4131-2005 " used for refractory material resol " supplemental provisions detects the free-phenol content in the said resol; Detect the free formaldehyde content in the said resol according to the vapor-phase chromatography in the mensuration of GB/T2912-1998 textile formaldehyde; Karl Fischer method according among the GB/T 6283-2008 " mensuration of moisture content in the Chemicals " detects moisture content in the said resol; Detect the gel time of said resol according to the pocket knife method among the GB/T24411-2009 " friction materials is used resol "; Use accurate combined electrode pH meter to detect the pH value of said resol; According to the viscosity of ISO 3219-1993 " the rotary viscosity design determining viscosity of plastics-liquid state or emulsion or dispersion liquid polymkeric substance-resin-usefulness regulation shearing rate " the said resol of mensuration, the result shows, in the resol that method provided by the invention prepares; Free phenol content in phenol less than 500ppm, content of free aldehyde in formaldehyde less than 500ppm.
The present invention removes free phenol and free aldehyde in the resol with the mode of chemical reaction; Make the content of free phenol and free aldehyde low as far as possible; Thereby when producing the dipping laminating material, the burst size of free phenol and free aldehyde is lower, to the pollution of environment and less to the injury of human body.
The present invention also provides a kind of low free phenol resol, in the said resol, free phenol content in phenol less than 500ppm, content of free aldehyde in formaldehyde less than 500ppm.
Said low free phenol resol is heat-reactive phenolic resin; Be applicable to and produce the dipping laminating material, because free phenol and content of free aldehyde are lower, when producing the dipping laminating material; The burst size of free phenol and free aldehyde is lower, and is less to the injury of the pollution of environment and human body.
The present invention is 1 with mol ratio at first: the phenol of (3～5) and aldehyde material are raw material, and reaction obtains the resol performed polymer under 20 ℃～70 ℃ low temperature environment; In said resol performed polymer, add formaldehyde reducing agent then, obtain all lower resol of free phenol and content of free aldehyde after the reaction.The present invention reacts with excessive aldehyde material and phenol at low temperatures, and phenol can react fully, thereby reduces the content of resol performed polymer middle reaches from phenol; In said resol performed polymer, add formaldehyde reducing agent then, formaldehyde reducing agent and excessive aldehyde material react, thereby reduce the content of free aldehyde in the resol.In the low free-phenol resol provided by the invention, the content of free phenol is counted below the 500ppm with phenol, and the content of free aldehyde is counted below the 500ppm with formaldehyde.Phenol in the resol provided by the invention and aldehyde material all take the method for chemical reaction to remove, and content is all lower, and be less to the harm of environment and HUMAN HEALTH.
In order to further specify the present invention, low free phenol resol provided by the invention and preparation method thereof is described in detail below in conjunction with embodiment.
Embodiment 1
1mol phenol, 3.5mol formaldehyde and 0.2mol sodium hydroxide are mixed, and 50 ℃ are reacted 8h down, obtain the phenolic aldehyde performed polymer; In said phenolic aldehyde performed polymer, add 0.4mol ammoniacal liquor, react to free formaldehyde content less than 500ppm, add hydrochloric acid and neutralize, with obtaining resol behind the reaction product filtration that obtains, washing, the decompression dehydration.
Said resol is carried out Performance Detection, and the result is referring to table 1, the performance test results of the resol that table 1 provides for the embodiment of the invention and comparative example.
Embodiment 2
With 1mol phenol, 5mol formaldehyde with contain the aqueous solution of 0.1mol Pottasium Hydroxide, 45 ℃ of reaction 6h down obtain the phenolic aldehyde performed polymer; In said phenolic aldehyde performed polymer, add the 0.5mol Hydrazine Hydrate 80, react to free formaldehyde content less than 500ppm, add hydrochloric acid and neutralize, with obtaining resol behind the reaction product filtration that obtains, washing, the decompression dehydration.
Said resol is carried out Performance Detection, and the result is referring to table 1, the performance test results of the resol that table 1 provides for the embodiment of the invention and comparative example.
Embodiment 3
1mol phenol, 4mol formaldehyde and 0.5mol ammoniacal liquor are mixed, and 70 ℃ are reacted 7h down, obtain the phenolic aldehyde performed polymer; In said phenolic aldehyde performed polymer, add 0.4mol urea, react to free formaldehyde content less than 500ppm, add hydrochloric acid and neutralize, with obtaining resol behind the reaction product filtration that obtains, washing, the decompression dehydration.
Said resol is carried out Performance Detection, and the result is referring to table 1, the performance test results of the resol that table 1 provides for the embodiment of the invention and comparative example.
Comparative example 1
With 1mol phenol, 2.5mol formaldehyde with contain the aqueous solution of 0.2mol sodium hydroxide, be warming up to 90 ℃ in the 60min, isothermal reaction 90min with the product decompression dehydration that obtains, obtains resol after adding dissolve with methanol.
Said resol is carried out Performance Detection, and the result is referring to table 1, the performance test results of the resol that table 1 provides for the embodiment of the invention and comparative example.
Comparative example 2
1mol phenol, 1mol formaldehyde and 0.1mol ammoniacal liquor are mixed, be warming up to 100 ℃ in the 60min, back flow reaction 120min to transparent, obtains resol behind the adding methyl alcohol with the product decompression dehydration that obtains.
Said resol is carried out Performance Detection, and the result is referring to table 1, the performance test results of the resol that table 1 provides for the embodiment of the invention and comparative example.
Comparative example 3
1mol phenol, 1mol formaldehyde and 0.1mol ammoniacal liquor are mixed, be warming up to 100 ℃ in the 60min, back flow reaction 120min; In the product that obtains, add 0.4mol urea, react to free formaldehyde content less than 500ppm, add hydrochloric acid and neutralize, with obtaining resol behind the product reaction product filtration that obtains, washing, the decompression dehydration.
Said resol is carried out Performance Detection, and the result is referring to table 1, the performance test results of the resol that table 1 provides for the embodiment of the invention and comparative example.
The performance test results of the resol that table 1 embodiment of the invention and comparative example provide
Can know by table 1; The resol that method provided by the invention prepares has the free-phenol and the free formaldehyde of lower aq; When being used for the preparation of laminating material, the volatilization of less generation free-phenol and free formaldehyde, thus can influence ecological environment, be detrimental to health.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (9)
1. the preparation method of a low free phenol resol may further comprise the steps:
A) phenol and aldehyde material react under 20 ℃～70 ℃, the condition of basic catalyst, obtain the phenolic aldehyde performed polymer, and the mol ratio of said phenol and aldehyde material is 1: (3～5);
B) in the phenolic aldehyde performed polymer that said step a) obtains, add formaldehyde reducing agent, obtain low free phenol resol after the reaction.
2. preparation method according to claim 1 is characterized in that, in the said step a), said aldehyde material is one or more in formaldehyde, trioxymethylene and the Paraformaldehyde 96.
3. preparation method according to claim 1; It is characterized in that; In the said step a); Said basic catalyst is one or more in sodium hydroxide, Pottasium Hydroxide, hydrated barta, Marinco H and the calcium hydroxide, perhaps is in ammoniacal liquor, alkylamine, dialkylamine, trialkylamine, aniline, diethylenetriamine, triethylene tetramine, hexamethylenetetramine, diethylolamine and the trolamine one or more.
4. preparation method according to claim 1 is characterized in that, in the said step a), the mol ratio of said basic catalyst and said phenol is (0.01～1): 1.
5. preparation method according to claim 1 is characterized in that, in the said step a), the time of said reaction is 1h～24h.
6. preparation method according to claim 1 is characterized in that, said step b) specifically comprises:
B1) in the phenolic aldehyde performed polymer that said step a) obtains, add formaldehyde reducing agent, reaction;
B2) to said step b1) add acid in the product that obtains and neutralize, obtain low free phenol resol.
7. preparation method according to claim 6; It is characterized in that; Said step b1) in; Said formaldehyde reducing agent is the verivate of ammoniacal liquor, Dyhard RU 100, trimeric cyanamide, an alkylamine, dialkylamine, trialkylamine, aniline, benzo guanamine, acetylguanamine, diethylenetriamine, triethylene tetramine, diethylolamine, trolamine, urea, urea, urea, one or more in Hydrazine Hydrate 80 and the hydrazine derivative.
8. preparation method according to claim 6 is characterized in that, said step b2) in, said acid is one or more in phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetate, oxalic acid, Whitfield's ointment and the toluenesulphonic acids.
9. one kind low free phenol resol, in the said resol, free phenol is below the 500ppm in phenol content, free aldehyde is below the 500ppm in formaldehyde content.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1585788A (en) * | 2001-11-21 | 2005-02-23 | 佐治亚·太平洋树脂公司 | Phenol-formaldehyde resin with low formaldehyde emission and its production method |
| CN101348548A (en) * | 2007-10-18 | 2009-01-21 | 李绍通 | Environment-friendly Process for Synthesizing Phenolic Resin |
| CN101704986A (en) * | 2009-11-19 | 2010-05-12 | 北京玻钢院复合材料有限公司 | Thermosetting phenolic resin cured and foamed rapidly at normal temperature, preparation method and application thereof |
| CN101935434A (en) * | 2010-08-25 | 2011-01-05 | 山东圣泉化工股份有限公司 | Preparation method of phenolic resins |
-
2011
- 2011-07-18 CN CN2011102002099A patent/CN102336878A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1585788A (en) * | 2001-11-21 | 2005-02-23 | 佐治亚·太平洋树脂公司 | Phenol-formaldehyde resin with low formaldehyde emission and its production method |
| CN101348548A (en) * | 2007-10-18 | 2009-01-21 | 李绍通 | Environment-friendly Process for Synthesizing Phenolic Resin |
| CN101704986A (en) * | 2009-11-19 | 2010-05-12 | 北京玻钢院复合材料有限公司 | Thermosetting phenolic resin cured and foamed rapidly at normal temperature, preparation method and application thereof |
| CN101935434A (en) * | 2010-08-25 | 2011-01-05 | 山东圣泉化工股份有限公司 | Preparation method of phenolic resins |
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