CN103602298B - Preparation method of phenolic resin adhesive - Google Patents
Preparation method of phenolic resin adhesive Download PDFInfo
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- CN103602298B CN103602298B CN201310377803.4A CN201310377803A CN103602298B CN 103602298 B CN103602298 B CN 103602298B CN 201310377803 A CN201310377803 A CN 201310377803A CN 103602298 B CN103602298 B CN 103602298B
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- phenolic resin
- rosin
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- polyborosiloxane
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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 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000853 adhesive Substances 0.000 title claims abstract description 17
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 17
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 14
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 14
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 65
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 65
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 65
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 63
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 21
- 150000007513 acids Chemical class 0.000 claims description 21
- 238000009833 condensation Methods 0.000 claims description 21
- 230000005494 condensation Effects 0.000 claims description 21
- 235000006408 oxalic acid Nutrition 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 16
- 239000004327 boric acid Substances 0.000 claims description 16
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 claims description 14
- 229920002545 silicone oil Polymers 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 11
- 235000013824 polyphenols Nutrition 0.000 claims description 9
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 7
- 238000005886 esterification reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 125000005375 organosiloxane group Chemical group 0.000 claims description 7
- 229940059574 pentaerithrityl Drugs 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- 230000004044 response Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 4
- 229960001755 resorcinol Drugs 0.000 claims description 4
- 238000004513 sizing Methods 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 2
- 229960001553 phloroglucinol Drugs 0.000 claims description 2
- 229940079877 pyrogallol Drugs 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920003987 resole Polymers 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000047 product 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to a preparation method of a phenolic resin adhesive. The preparation method is characterized by comprising a first step of synthesizing polyborosiloxane, a second step of synthesizing a rosin modified phenolic resin, and a third step of preparing the adhesive. In the preparation method, a preparation method of the polyborosiloxane has mild conditions, simple operation, no generation of harmful gases, and capability of environmental protection. The polyborosiloxane obtained has excellent high-temperature resistance. The adhesive with better adhesive performances is provided by combining the polyborosiloxane and the rosin modified phenolic resin, and has a good application prospect.
Description
Technical field
The invention belongs to chemical field, relate in particular to a kind of preparation method of phenolic resin adhesive.
Background technology
Polyborosiloxane has excellent resistance toheat.There are research and utilization boric acid and organosilicon preformed polymer to prepare polyborosiloxane, and use it for the modification of resol, resin carbon residue rate after modification significantly improves, (the Zhang Bin etc. but the cohesive force of the phenolic resin adhesive after modification is not significantly improved, polymer material science and engineering, 2008,152).There is research in polyborosiloxane, to introduce Resorcinol structure, obtain polyborosiloxane, the following technological line preparation of main employing at present: application melt-polycondensation, polyborosiloxane is carried out to modification with Resorcinol, obtain high temperature resistant polyborosiloxane (Zhan Hongwei, Cao Jin, Journal of Functional Polymers .1995,8,439).In above-mentioned route, there is following problem: its severe reaction conditions, need 300 DEG C of high temperature, very high to vacuum tightness requirement, also very high to equipment and personnel's technical requirements.
Resol price is very low, raw material has easily been bought, production technique and production unit simple, become one of indispensable material of industrial sector, apply very extensive.Pure phenolic aldehyde resin thermal stability and high thermal resistance are not high enough, and after modification, the impelling strength of resol, cementability, physical strength, thermotolerance, flame retardant resistance, dimensional stability, curing speed, moulded manufacturability etc., be improved respectively.
Summary of the invention
The present invention has designed a kind of preparation method of phenolic resin adhesive, its object is the resol after Abietyl modified to be combined with polyborosiloxane and to provide a kind of bond properties better sizing agent,, the preparation method of polyborosiloxane is improved meanwhile, overcome the problems of the prior art.
To achieve these goals, the present invention has adopted following scheme:
A preparation method for phenolic resin adhesive, is characterized in that comprising following steps:
Step 1: synthetic polyborosiloxane;
Step 2: synthetic rosin modified phenolic resin;
Step 3: prepare sizing agent.
Described step 1 is that organo-siloxane and boric acid are joined in organic solvent, under the condition existing, in lower 3 hours of nitrogen atmosphere, is progressively warmed up to 140 DEG C from 90 DEG C at catalyzer, continues reaction 4h; Then add polyphenol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane;
Described step 2 is that rosin is added in reactor, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added to reactor; heat to 150 DEG C; pressure is brought up to 0.7Mpa, reacts 2 hours under constant temperature and pressure, obtains rosin condensation intermediate; Then the reactor that tetramethylolmethane, triethylamine and dimethyl silicone oil is added to rosin condensation intermediate, is warmed up to 200 DEG C, and pressure is controlled to 0.1Mpa, starts agitator and stirs, and constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin;
Described step 3 is to get the rosin modified phenolic resin that the polyborosiloxane that makes in step 1 and step 2 make to mix by the mass ratio of 0.1-1:2, obtains synvaren.
Organo-siloxane described in step 1: boric acid: the mol ratio of polyphenol is 1:1～2:0.25～1, catalyst levels is 1 ‰ of monomer total mass.
Described in step 1, organo-siloxane is vinyltrimethoxy silane.
Described in step 1, solvent is diethylene glycol dimethyl ether or dioxane.
Described in step 1, catalyzer is any one in tin protochloride, titanium tetrachloride, Indian red.
Polyphenol described in step 1 is a kind of or several mixing in pyrocatechol, Resorcinol, Resorcinol, Phloroglucinol, pyrogallol.
Formaldehyde in rosin condensation intermediate preparation described in step 2: 4-dodecylphenol: rosin mol ratio is 5:2:7.
Oxalic acid described in step 2 and toluenesulphonic acids mass ratio are 1:1, and the overall add-on of described oxalic acid and toluenesulphonic acids is rosin quality 0.15%.
Described in step 3, the mass ratio of polyborosiloxane and rosin modified phenolic resin is 0.3-1:2.
The preparation method of this phenolic resin adhesive has following beneficial effect:
1, the inventive method can complete at a reactor preparation of rosin modified phenolic resin and series product, has reduced facility investment.
2, the present invention is by organo-siloxane and boric acid, polyphenol polycondensation, the synthetic polyborosiloxane that contains a large amount of terminal hydroxy group and have excellent heat resistance; After mixing with resol, can improve its thermotolerance and bonding strength.
3, the present invention prepares polyborosiloxane method mild condition, simple to operate, without harmful gas generation, environmental protection, and gained polyborosiloxane resistance to elevated temperatures excellence, overall craft route of the present invention is simple, greatly reduces energy consumption.
4, the present invention does not have by product and waste water and gas discharge in reaction process, is a kind of production process of environmental protection.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described:
Embodiment 1
The preparation method of phenolic resin adhesive of the present invention
Step 1 is that vinyltrimethoxy silane and boric acid are joined in diethylene glycol dimethyl ether, under the condition existing, in lower 3 hours of nitrogen atmosphere, is progressively warmed up to 140 DEG C from 90 DEG C at tin protochloride, continues reaction 4h; Then add pyrocatechol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane; Vinyltrimethoxy silane: boric acid: the mol ratio of pyrocatechol is 1:1:0.5, tin protochloride consumption is 1 ‰ of monomer total mass.
Step 2 is that rosin is added in reactor, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added to reactor; heat to 150 DEG C; pressure is brought up to 0.7Mpa, reacts 2 hours under constant temperature and pressure, obtains rosin condensation intermediate; Then the reactor that tetramethylolmethane, triethylamine and dimethyl silicone oil is added to rosin condensation intermediate, is warmed up to 200 DEG C, and pressure is controlled to 0.1Mpa, starts agitator and stirs, and constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin; Formaldehyde in the preparation of rosin condensation intermediate: 4-dodecylphenol: rosin mol ratio is 5:2:7.Oxalic acid and toluenesulphonic acids mass ratio are 1:1, and the overall add-on of oxalic acid and toluenesulphonic acids is rosin quality 0.15%.
Step 3 is to get the rosin modified phenolic resin that the polyborosiloxane that makes in step 1 and step 2 make to mix by the mass ratio of 0.3:2, obtains synvaren.
Embodiment 2
Step 1 is that vinyltrimethoxy silane and boric acid are joined in diethylene glycol dimethyl ether, under the condition existing, in lower 3 hours of nitrogen atmosphere, is progressively warmed up to 140 DEG C from 90 DEG C at titanium tetrachloride, continues reaction 4h; Then add pyrocatechol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane; Vinyltrimethoxy silane: boric acid: the mol ratio of pyrocatechol is 1:1:0.5, titanium tetrachloride consumption is 1 ‰ of monomer total mass.
Step 2 is that rosin is added in reactor, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added to reactor; heat to 150 DEG C; pressure is brought up to 0.7Mpa, reacts 2 hours under constant temperature and pressure, obtains rosin condensation intermediate; Then the reactor that tetramethylolmethane, triethylamine and dimethyl silicone oil is added to rosin condensation intermediate, is warmed up to 200 DEG C, and pressure is controlled to 0.1Mpa, starts agitator and stirs, and constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin; Formaldehyde in the preparation of rosin condensation intermediate: 4-dodecylphenol: rosin mol ratio is 5:2:7.Oxalic acid and toluenesulphonic acids mass ratio are 1:1, and the overall add-on of oxalic acid and toluenesulphonic acids is rosin quality 0.15%.
Step 3 is to get the rosin modified phenolic resin that the polyborosiloxane that makes in step 1 and step 2 make to mix by the mass ratio of 0.5:2, obtains synvaren.
Embodiment 3
Step 1 is that vinyltrimethoxy silane and boric acid are joined in diethylene glycol dimethyl ether, under the condition existing, in lower 3 hours of nitrogen atmosphere, is progressively warmed up to 140 DEG C from 90 DEG C at Indian red, continues reaction 4h; Then add pyrocatechol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane; Vinyltrimethoxy silane: boric acid: the mol ratio of pyrocatechol is 1:1:0.5, Indian red consumption is 1 ‰ of monomer total mass.
Step 2 is that rosin is added in reactor, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added to reactor; heat to 150 DEG C; pressure is brought up to 0.7Mpa, reacts 2 hours under constant temperature and pressure, obtains rosin condensation intermediate; Then the reactor that tetramethylolmethane, triethylamine and dimethyl silicone oil is added to rosin condensation intermediate, is warmed up to 200 DEG C, and pressure is controlled to 0.1Mpa, starts agitator and stirs, and constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin; Formaldehyde in the preparation of rosin condensation intermediate: 4-dodecylphenol: rosin mol ratio is 5:2:7.Oxalic acid and toluenesulphonic acids mass ratio are 1:1, and the overall add-on of oxalic acid and toluenesulphonic acids is rosin quality 0.15%.
Step 3 is to get the rosin modified phenolic resin that the polyborosiloxane that makes in step 1 and step 2 make to mix by the mass ratio of 0.6:2, obtains synvaren.
Embodiment 4
Step 1 is that vinyltrimethoxy silane and boric acid are joined in dioxane, under the condition existing, in lower 3 hours of nitrogen atmosphere, is progressively warmed up to 140 DEG C from 90 DEG C at titanium tetrachloride, continues reaction 4h; Then add pyrocatechol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane; Vinyltrimethoxy silane: boric acid: the mol ratio of pyrocatechol is 1:1:0.5, titanium tetrachloride consumption is 1 ‰ of monomer total mass.
Step 2 is that rosin is added in reactor, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added to reactor; heat to 150 DEG C; pressure is brought up to 0.7Mpa, reacts 2 hours under constant temperature and pressure, obtains rosin condensation intermediate; Then the reactor that tetramethylolmethane, triethylamine and dimethyl silicone oil is added to rosin condensation intermediate, is warmed up to 200 DEG C, and pressure is controlled to 0.1Mpa, starts agitator and stirs, and constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin; Formaldehyde in the preparation of rosin condensation intermediate: 4-dodecylphenol: rosin mol ratio is 5:2:7.Oxalic acid and toluenesulphonic acids mass ratio are 1:1, and the overall add-on of oxalic acid and toluenesulphonic acids is rosin quality 0.15%.
Step 3 is to get the rosin modified phenolic resin that the polyborosiloxane that makes in step 1 and step 2 make to mix by the mass ratio of 0.8:2, obtains synvaren.
Embodiment 5
Step 1 is that vinyltrimethoxy silane and boric acid are joined in dioxane, under the condition existing, in lower 3 hours of nitrogen atmosphere, is progressively warmed up to 140 DEG C from 90 DEG C at Indian red, continues reaction 4h; Then add pyrocatechol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane; Vinyltrimethoxy silane: boric acid: the mol ratio of pyrocatechol is 1:1:0.5, Indian red consumption is 1 ‰ of monomer total mass.
Step 2 is that rosin is added in reactor, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added to reactor; heat to 150 DEG C; pressure is brought up to 0.7Mpa, reacts 2 hours under constant temperature and pressure, obtains rosin condensation intermediate; Then the reactor that tetramethylolmethane, triethylamine and dimethyl silicone oil is added to rosin condensation intermediate, is warmed up to 200 DEG C, and pressure is controlled to 0.1Mpa, starts agitator and stirs, and constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin; Formaldehyde in the preparation of rosin condensation intermediate: 4-dodecylphenol: rosin mol ratio is 5:2:7.Oxalic acid and toluenesulphonic acids mass ratio are 1:1, and the overall add-on of oxalic acid and toluenesulphonic acids is rosin quality 0.15%.
Step 3 is to get the rosin modified phenolic resin that the polyborosiloxane that makes in step 1 and step 2 make to mix by the mass ratio of 1:2, obtains synvaren.
Polyphenol in above-described embodiment 1-5 has all been selected pyrocatechol, in the essentially identical situation of all the other conditions, only change the reaction ratio of polyborosiloxane and rosin modified phenolic resin, then to the product obtaining in embodiment through gluing, solidify, measure its cohesive strength.Experimental result shows, the cohesive strength maximum of the sizing agent obtaining in the time that polyborosiloxane and rosin modified phenolic resin mix by the mass ratio of 0.8:2.
In conjunction with specific embodiments the present invention is carried out to exemplary description above; obvious realization of the present invention is not subject to the restrictions described above; as long as the various improvement that adopted method design of the present invention and technical scheme to carry out; or without improving, design of the present invention and technical scheme are directly applied to other occasion, all in protection scope of the present invention.
Claims (5)
1. a preparation method for phenolic resin adhesive, comprises following steps: step 1: synthetic polyborosiloxane; Step 2: synthetic rosin modified phenolic resin; Step 3: prepare sizing agent; Described step 1 is that organo-siloxane and boric acid are joined in organic solvent, under the condition existing, in lower 3 hours of nitrogen atmosphere, is progressively warmed up to 140 DEG C from 90 DEG C at catalyzer, continues reaction 4h; Then add polyphenol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane; Organo-siloxane described in step 1: boric acid: the mol ratio of polyphenol is 1:1～2:0.25～1, catalyst levels is 1 ‰ of monomer total mass; Described in step 1, organo-siloxane is vinyltrimethoxy silane; Described in step 1, solvent is diethylene glycol dimethyl ether or dioxane; Described in step 1, catalyzer is any one in tin protochloride, titanium tetrachloride, Indian red; Described step 2 is that rosin is added in reactor, and heating is dissolved and stirs, and heats to 95 DEG C; Add 4-dodecylphenol, be stirred to and dissolve completely and mix, formaldehyde, dimethyl silicone oil, oxalic acid and toluenesulphonic acids are added to reactor; heat to 150 DEG C; pressure is brought up to 0.7Mpa, reacts 2 hours under constant temperature and pressure, obtains rosin condensation intermediate; Then the reactor that tetramethylolmethane, triethylamine and dimethyl silicone oil is added to rosin condensation intermediate, is warmed up to 200 DEG C, and pressure is controlled to 0.1Mpa, starts agitator and stirs, and constant temperature and pressure carries out esterification 4 hours, obtains rosin modified phenolic resin; Described step 3 is to get the rosin modified phenolic resin that the polyborosiloxane that makes in step 1 and step 2 make to mix by the mass ratio of 0.1-1:2, obtains synvaren.
2. the preparation method of phenolic resin adhesive according to claim 1, is characterized in that: the polyphenol described in step 1 is a kind of or several mixing in pyrocatechol, Resorcinol, Resorcinol, Phloroglucinol, pyrogallol.
3. the preparation method of phenolic resin adhesive according to claim 1, is characterized in that: formaldehyde in the rosin condensation intermediate preparation described in step 2: 4-dodecylphenol: rosin mol ratio is 5:2:7.
4. the preparation method of phenolic resin adhesive according to claim 1, is characterized in that: oxalic acid described in step 2 and toluenesulphonic acids mass ratio are 1:1, and the overall add-on of described oxalic acid and toluenesulphonic acids is rosin quality 0.15%.
5. the preparation method of phenolic resin adhesive according to claim 1, is characterized in that: described in step 3, the mass ratio of polyborosiloxane and rosin modified phenolic resin is 0.3-1:2.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410801413.XA CN104559868B (en) | 2013-08-27 | 2013-08-27 | A kind of preparation method of phenolic resin adhesive |
| CN201410801309.0A CN104559866B (en) | 2013-08-27 | 2013-08-27 | A kind of preparation method of phenolic resin adhesive |
| CN201410801412.5A CN104559867B (en) | 2013-08-27 | 2013-08-27 | A kind of preparation method of phenolic resin adhesive |
| CN201310377803.4A CN103602298B (en) | 2013-08-27 | 2013-08-27 | Preparation method of phenolic resin adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310377803.4A CN103602298B (en) | 2013-08-27 | 2013-08-27 | Preparation method of phenolic resin adhesive |
Related Child Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410801309.0A Division CN104559866B (en) | 2013-08-27 | 2013-08-27 | A kind of preparation method of phenolic resin adhesive |
| CN201410801412.5A Division CN104559867B (en) | 2013-08-27 | 2013-08-27 | A kind of preparation method of phenolic resin adhesive |
| CN201410801413.XA Division CN104559868B (en) | 2013-08-27 | 2013-08-27 | A kind of preparation method of phenolic resin adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103602298A CN103602298A (en) | 2014-02-26 |
| CN103602298B true CN103602298B (en) | 2014-11-26 |
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| CN105348459B (en) * | 2015-12-11 | 2017-08-25 | 华奇（中国）化工有限公司 | Abietyl modified resorcinol formaldehyde resin and its preparation method and application |
| CN107793973A (en) * | 2017-11-29 | 2018-03-13 | 广西众昌树脂有限公司 | Modified phenolic resin adhesive and preparation method thereof |
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| CN102746479A (en) * | 2011-04-19 | 2012-10-24 | 襄樊学院 | Preparation method of boron-containing phenolic resin for friction materials |
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| CN104559866A (en) | 2015-04-29 |
| CN104559866B (en) | 2016-06-22 |
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| CN104559868A (en) | 2015-04-29 |
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