CN104804194A - Method for preparing TiBSi and modifying phenolic resin - Google Patents
Method for preparing TiBSi and modifying phenolic resin Download PDFInfo
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- CN104804194A CN104804194A CN201510233922.1A CN201510233922A CN104804194A CN 104804194 A CN104804194 A CN 104804194A CN 201510233922 A CN201510233922 A CN 201510233922A CN 104804194 A CN104804194 A CN 104804194A
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- borosiloxane
- titanium
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- butyl
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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 19
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229920001568 phenolic resin Polymers 0.000 title abstract description 9
- 239000005011 phenolic resin Substances 0.000 title abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 17
- 239000000853 adhesive Substances 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 57
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- 229910052719 titanium Inorganic materials 0.000 claims description 34
- 239000010936 titanium Substances 0.000 claims description 34
- 229920003987 resole Polymers 0.000 claims description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 26
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 229920003986 novolac Polymers 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000005815 base catalysis Methods 0.000 claims description 10
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 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
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 abstract 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract 1
- -1 phenol aldehyde Chemical class 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000007711 solidification Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a method for preparing TiBSi and modifying phenolic resin, belonging to the technical field of macromolecular materials. The method comprises the following steps of firstly reacting polyborosiloxane, butyl titanate, acetylacetone and linear phenol aldehyde so as to synthesize the TiBSi, blending the TiBSi with base-catalyzed phenolic resin for modification, and obtaining a modified phenolic resin adhesive with high temperature resistance and high bonding strength.
Description
Technical field
The present invention relates to a kind of poly-titanium Borosiloxane preparation and to phenolic resin modified method.Be specifically related to polyborosiloxane and butyl (tetra) titanate, methyl ethyl diketone, novolac react jointly, the poly-titanium Borosiloxane of synthesis, and modification is carried out to base catalysis resol, improve its adhesiveproperties and its thermotolerance, belong to technical field of polymer materials.
Technical background
Resol is cheap, raw material is easy to get, production technique and production unit simple, has become one of indispensable material of industrial sector, and application widely.Pure resol adhesiveproperties and high thermal resistance not high enough, people have carried out large quantity research to its modification, to improve its cohesive strength and thermotolerance.
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, modified resin carbon yield significantly improves, but the cohesive force of modified phenolic resin adhesive does not significantly improve (Zhang Bin etc., polymer material science and engineering, 2008,152).Butyl (tetra) titanate can provide Quick cross-linking to react, the binding property of polymkeric substance can be improved, and resistance to elevated temperatures (Shi-hong Shen.et al, the Polymer Degradation andStability of resol can be improved to a certain extent, 2013,514).There is research in resol, introduce more Resorcinol, can obtain containing more polyhydric structure, but the more difficult whole and reactive modified phenolic resin of the Resorcinol newly added.The resol cementability modified with Resorcinol increases, but thermotolerance poor (Chunxia WANG etc., forestry machinery and woodworking equipment, 2014,13).
There are some problems in above-mentioned method, due to the unicity of raw material, the thermotolerance both having improved resol cannot be met, improve again the cementability of resol.
Summary of the invention
An object of the present invention, is to provide a kind of high temperature resistant poly-titanium Borosiloxane (TiBSi) preparation method of simple to operate, excellent performance; Object two, provides a kind of cohesive force strong, resistant to elevated temperatures modified phenolic resin adhesive.
First the present invention reacts at a lower temperature with polyborosiloxane, butyl (tetra) titanate, methyl ethyl diketone and novolac, obtains the poly-titanium Borosiloxane containing a large amount of terminal hydroxy group, itself has good high thermal resistance; Then by this poly-titanium Borosiloxane and resol compound, modified phenolic resin adhesive is obtained.
Technical scheme of the present invention is:
The preparation method of poly-titanium Borosiloxane, it is characterized in that, comprise the following steps: the preparation of poly-titanium Borosiloxane (TiBSi): first by novolac and butyl (tetra) titanate inner complex admixed together in the presence of the solvent, again this mixture is joined in polyborosiloxane, under nitrogen atmosphere, 60 DEG C of low-temp reaction 5h, water pump decompression 0.5 ~ 1h; Wherein butyl (tetra) titanate inner complex is that butyl (tetra) titanate and methyl ethyl diketone equimolar ratio are reacted and formed, polyborosiloxane: the butyl (tetra) titanate comprised in butyl (tetra) titanate inner complex: novolac mass ratio is 1:(0.2 ~ 0.6): 1.
Raw material polyborosiloxane, for the one in Union carbide A-162, methyltrimethoxy silane, ethyl triethoxysilane, ethyl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane and boric acid are by (1 ~ 2): 1 molar ratio reaction is prepared and generated.Preferably press (1 ~ 2) with phenyltrimethoxysila,e and boric acid: 1 mol ratio is reacted 3 ~ 5h at 140-150 DEG C and is prepared from, and number-average molecular weight is about 800.
Butyl (tetra) titanate mixes with methyl ethyl diketone equimolar ratio, first forms inner complex, to reduce butyl (tetra) titanate activity, is convenient to the carrying out of subsequent reactions.
Novolac is preferably by the one in phenol, pyrocatechol, Resorcinol, Resorcinol, Phloroglucinol, pyrogallol or to be severally prepared from formalin solution, and number-average molecular weight is about 600.
Described solvent is diethylene glycol dimethyl ether, dioxane, tetrahydrofuran (THF), N, any one of N '-dimethyl methane amide.
Adopt poly-titanium Borosiloxane of the present invention to the phenolic resin modified method preparing modified phenolic resin adhesive, preferably include following steps: will titanium Borosiloxane and base catalysis resol PF be gathered by (0.5 ~ 1): the mass ratio of 1 mixes, and obtains the synvaren of poly-titanium Borosiloxane modification.
The synthesis of above-mentioned base catalysis resol PF, preferred: with phenol and formaldehyde in molar ratio for 1:1.5, the consumption of alkaline catalysts is 6 ‰ of total mass, reaction is slowly warmed up to 90 DEG C from 40 DEG C, be incubated 1.5 hours, then cool to 60 ~ 70 DEG C, water pump decompression steams water, obtains base catalysis resol PF.Described alkaline catalysts is the one in sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate and hydrated barta.
By modified phenolic resin adhesive through gluing, solidification, measure its carbon yield and cohesive strength.
Effect of the present invention:
The present invention is by polyborosiloxane, butyl (tetra) titanate, methyl ethyl diketone, novolac reaction, and synthesis contains a large amount of terminal hydroxy group and has the poly-titanium Borosiloxane (TiBSi) of excellent heat resistance; After mixing with resol, its bonding strength and thermotolerance can be improved.Gather during solidification terminal hydroxy group a large amount of in titanium Borosiloxane can with resol generation polycondensation, and wherein containing a large amount of silica, boron oxygen, titanyl structure, be beneficial to and improve its cohesive strength and thermostability.
The preparation method of poly-titanium Borosiloxane briefly schematically illustrates as follows:
The present invention prepares poly-titanium Borosiloxane method mild condition (60 DEG C), simple to operate, lower to equipment requirements, gained gathers titanium Borosiloxane resistance to elevated temperatures excellence, containing a large amount of terminal hydroxy group, as properties-correcting agent, cohesive strength and the high thermal resistance of resol can be improved, for the intensity and resistance to elevated temperatures improving phenolic resin adhesive provides a kind of feasible method simultaneously.
Embodiment
The present invention is with polyborosiloxane, butyl (tetra) titanate, methyl ethyl diketone, novolac for raw material, and obtained poly-titanium Borosiloxane, then carries out modification to resol, obtains the higher and modified phenolic resin adhesive of 800 DEG C higher compared with carbon yield of bonding strength.
Below in conjunction with specific embodiment, the invention will be further described, but protection of the present invention is not limited to the scope involved by embodiment.
Polyborosiloxane phenyltrimethoxysila,e and boric acid are by (1 ~ 2): 1 mol ratio is reacted 3 ~ 5h at 140-150 DEG C and is prepared from, and number-average molecular weight is about 800.
The following stated mark is mass fraction.
Embodiment 1:
The preparation of poly-titanium Borosiloxane: polyborosiloxane is (by phenyltrimethoxysila,e and boric acid 1:1 in molar ratio, in a nitrogen environment, in 150 DEG C of reactions 3 hours, and deviate from solvent and be prepared from) 1 part (being dissolved in 10 parts of tetrahydrofuran (THF)s), inner complex containing butyl (tetra) titanate 0.2 part (is dissolved in 10 parts of tetrahydrofuran (THF)s, inner complex is formed with a mole methyl ethyl diketone such as grade by the butyl (tetra) titanate of 0.2 part), novolac (prepared under the condition of careless acid as catalyst by phenol and formalin solution, wherein phenol and formaldehyde mole ratio are 1:0.9) 1 part (being dissolved in 10 parts of tetrahydrofuran (THF)s), three is admixed together, 60 DEG C are progressively warmed up to from room temperature in a nitrogen atmosphere in 2h, reaction 5h, water pump Depressor response 0.5 ~ 1h, obtain poly-titanium Borosiloxane.
Embodiment 2:
The preparation of poly-titanium Borosiloxane: polyborosiloxane is (by phenyltrimethoxysila,e and boric acid 1:1 in molar ratio, in a nitrogen environment, in 150 DEG C of reactions 3 hours, and deviate from solvent and be prepared from) 1 part (being dissolved in 10 parts of tetrahydrofuran (THF)s), inner complex containing butyl (tetra) titanate 0.4 part (is dissolved in 10 parts of tetrahydrofuran (THF)s, inner complex is formed with a mole methyl ethyl diketone such as grade by the butyl (tetra) titanate of 0.4 part), novolac (prepared under the condition of careless acid as catalyst by phenol and formalin solution, wherein phenol and formaldehyde mole ratio are 1:0.9) 1 part (being dissolved in 10 parts of tetrahydrofuran (THF)s), three is admixed together, 60 DEG C are progressively warmed up to from room temperature in a nitrogen atmosphere in 2h, reaction 5h, water pump Depressor response 0.5 ~ 1h, obtain poly-titanium Borosiloxane.
Embodiment 3:
The preparation of poly-titanium Borosiloxane: polyborosiloxane is (by phenyltrimethoxysila,e and boric acid 1:1 in molar ratio, in a nitrogen environment, in 150 DEG C of reactions 3 hours, and deviate from solvent and be prepared from) 1 part (being dissolved in 10 parts of tetrahydrofuran (THF)s), inner complex containing butyl (tetra) titanate 0.6 part (is dissolved in 10 parts of tetrahydrofuran (THF)s, inner complex is formed with a mole methyl ethyl diketone such as grade by the butyl (tetra) titanate of 0.6 part), novolac (prepared under the condition of careless acid as catalyst by phenol and formalin solution, wherein phenol and formaldehyde mole ratio are 1:0.9) 1 part (being dissolved in 10 parts of tetrahydrofuran (THF)s), three is admixed together, 60 DEG C are progressively warmed up to from room temperature in a nitrogen atmosphere in 2h, reaction 5h, water pump Depressor response 0.5 ~ 1h, obtain poly-titanium Borosiloxane.
Embodiment 1-3 gained gather titanium Borosiloxane molecular weight and at the carbon yield of 800 DEG C in table 1.As can be seen from the table, in embodiment 1 ~ 3, the number-average molecular weight of the poly-titanium Borosiloxane of gained is between 850 ~ 870, and between 800 DEG C of carbon yield 71.40-71.69%, difference is little.
Table 1 embodiment 1-3 gained gathers molecular weight and the carbon yield of titanium Borosiloxane
Embodiment 4:
The synthesis of base catalysis resol: take hydrated barta as catalyzer, it is the hydrated barta mixing of the phenol of 43.6 parts, the formaldehyde solution of 56.4 part 36% and 0.6 part by massfraction, 90 DEG C are slowly warmed up to by 40 DEG C, be incubated 1.5 hours, then 60 ~ 70 DEG C are cooled to, water pump decompression steams the water that reaction generates, and obtains base catalysis resol PF.
Embodiment 5:
The preparation of modified phenolic resin adhesive and test: mix with the resol 1 part (weight part) of the poly-titanium Borosiloxane 1 part (weight part) obtained in embodiment 1 and embodiment 4, stir, get a part and be used as adhesive solidification, another part directly solidifies, condition of cure is 150 DEG C, solidification 4h.And contrast with the self cure of alkali phenolic resin adhesive.
Embodiment 6:
The preparation of modified phenolic resin adhesive and test: mix with the resol 2 parts (weight parts) of the poly-titanium Borosiloxane 1 part (weight part) obtained in embodiment 1 and embodiment 4, stir, get a part and be used as adhesive solidification, another part directly solidifies, condition of cure is 150 DEG C, solidification 4h.
Modified phenolic resins after the solidification of embodiment 5-6 gained, contrasts with the solidification of embodiment 4 gained resol, adopts TGA and stretch to measure its carbon yield and cohesive strength, in table 2.Phenolic resin adhesive is modified through poly-titanium Borosiloxane, and bonding strength is improved significantly, and 800 DEG C of Residual carbon also achieve certain raising.As TiBSi:PF (mass ratio)=1:2, bonding strength is up to 6.32MPa, and carbon yield can reach 70.18%.
| Numbering | TiBSi:PF (mass ratio) | Shearing resistance (MPa) | 800 DEG C of carbon yields (%) |
| Example 4 | 0:1 | 4.41 | 64.79 |
| Example 5 | 1:1 | 6.22 | 69.72 |
| Example 6 | 1:2 | 6.32 | 70.18 |
Claims (8)
1. the preparation method of a poly-titanium Borosiloxane (TiBSi), it is characterized in that, comprise the following steps: first by novolac and butyl (tetra) titanate inner complex admixed together in the presence of a solvent, again this mixture is joined in polyborosiloxane, under nitrogen atmosphere, 60 DEG C of low-temp reaction 5h, water pump decompression 0.5 ~ 1h; Wherein butyl (tetra) titanate inner complex is that butyl (tetra) titanate and methyl ethyl diketone equimolar ratio are reacted and formed, polyborosiloxane: the butyl (tetra) titanate comprised in butyl (tetra) titanate inner complex: novolac mass ratio is 1:(0.2 ~ 0.6): 1.
2. according to the method for claim 1, it is characterized in that, raw material polyborosiloxane, for the one in Union carbide A-162, methyltrimethoxy silane, ethyl triethoxysilane, ethyl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane and boric acid are by (1 ~ 2): 1 molar ratio reaction is prepared and generated.
3. according to the method for claim 1, it is characterized in that, novolac phenol, pyrocatechol, Resorcinol, Resorcinol, Phloroglucinol, pyrogallol are a kind of or several to be prepared from formalin solution.
4. according to the method for claim 1, it is characterized in that, described solvent is diethylene glycol dimethyl ether, dioxane, tetrahydrofuran (THF), N, any one of N '-dimethyl methane amide.
5. the method that the poly-titanium Borosiloxane (TiBSi) utilizing the method for claim 1 to prepare is heat resistance modified to resol, it is characterized in that, comprise the following steps: get poly-titanium Borosiloxane and base catalysis resol PF by (0.5 ~ 1): the mass ratio of 1 mixes, and obtains poly-titanium Borosiloxane modified phenolic resin adhesive.
6. according to the method for claim 5, it is characterized in that, the mass ratio 1:1 of poly-titanium Borosiloxane and base catalysis resol PF.
7. according to the method for claim 5, it is characterized in that, the synthesis of base catalysis resol PF, with phenol and formaldehyde in molar ratio for 1:1.5, the consumption of alkaline catalysts is 6 ‰ of total mass, reacts and is slowly warmed up to 90 DEG C from 40 DEG C, be incubated 1.5 hours, then cool to 60 ~ 70 DEG C, water pump decompression steams water, obtains base catalysis resol PF.
8. according to the method for claim 7, it is characterized in that, described alkaline catalysts is the one in sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate and hydrated barta.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467252A (en) * | 2018-05-18 | 2018-08-31 | 安徽朗凯奇建材有限公司 | A kind of high temperature resistant curing agent floor material and its preparation process |
| CN109160988A (en) * | 2018-10-11 | 2019-01-08 | 北京玻钢院复合材料有限公司 | The preparation method of titanium-modified phenolic resin |
| CN110498972A (en) * | 2019-09-26 | 2019-11-26 | 金发科技股份有限公司 | Purposes of the polyaluminosiloxane polymer as surface tension modifier |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108467252A (en) * | 2018-05-18 | 2018-08-31 | 安徽朗凯奇建材有限公司 | A kind of high temperature resistant curing agent floor material and its preparation process |
| CN109160988A (en) * | 2018-10-11 | 2019-01-08 | 北京玻钢院复合材料有限公司 | The preparation method of titanium-modified phenolic resin |
| CN110498972A (en) * | 2019-09-26 | 2019-11-26 | 金发科技股份有限公司 | Purposes of the polyaluminosiloxane polymer as surface tension modifier |
| CN110498972B (en) * | 2019-09-26 | 2021-10-15 | 金发科技股份有限公司 | Use of polyaluminosiloxane polymers as surface tension modifiers |
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