CN104804194B - The preparation of poly- titanium Borosiloxane and the method for modifying to phenolic resin - Google Patents
The preparation of poly- titanium Borosiloxane and the method for modifying to phenolic resin Download PDFInfo
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- CN104804194B CN104804194B CN201510233922.1A CN201510233922A CN104804194B CN 104804194 B CN104804194 B CN 104804194B CN 201510233922 A CN201510233922 A CN 201510233922A CN 104804194 B CN104804194 B CN 104804194B
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- phenolic resin
- borosiloxane
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- titanium
- butyl titanate
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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 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 37
- 239000010936 titanium Substances 0.000 title claims abstract description 37
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 35
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920003986 novolac Polymers 0.000 claims abstract description 14
- 238000005815 base catalysis Methods 0.000 claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- 230000001070 adhesive effect Effects 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000013522 chelant Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 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 8
- 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 group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- -1 Acyl acetone Chemical compound 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000002994 raw material Substances 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
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims description 2
- 239000000203 mixture 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
- 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 group CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 229960003742 phenol Drugs 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 abstract description 40
- 239000002861 polymer material Substances 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002148 esters Chemical class 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
- 239000003292 glue Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 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
- 229920001807 Urea-formaldehyde Polymers 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
- 229920000180 alkyd Polymers 0.000 description 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229960005222 phenazone Drugs 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The preparation of poly- titanium Borosiloxane and the method for modifying to phenolic resin, belong to technical field of polymer materials.First polyborosiloxane, butyl titanate, acetylacetone,2,4-pentanedione, novolac are reacted, poly- titanium Borosiloxane is synthesized, it is mixed with base catalysis phenolic resin and is modified, high temperature resistant, the phenoweld of high-adhesive-strength is obtained.
Description
Technical field
The present invention relates to a kind of preparation of poly- titanium Borosiloxane and to phenolic resin modified method.Specifically related to poly- borosilicate
Oxygen alkane reacts jointly with butyl titanate, acetylacetone,2,4-pentanedione, novolac, synthesizes poly- titanium Borosiloxane, and to base catalysis phenolic resin
It is modified, improves its adhesive property and its heat resistance, belong to technical field of polymer materials.
Technical background
Phenolic resin is cheap, raw material is easy to get, production technology and production equipment are simple, it has also become industrial department is indispensable
One of few material, using widely.Pure phenolic resin adhesive property and heat-resisting quantity are not high enough, people it is modified into
Numerous studies are gone, to improve its adhesion strength and heat resistance.
Polyborosiloxane has excellent heat resistance.There is research and utilization boric acid with organosilicon preformed polymer to prepare poly- borosilicate
Oxygen alkane, and the modification of phenolic resin is used it for, modified resin carbon yield is greatly improved, but modified phenolic resin glue
The cohesive force of glutinous agent does not significantly improve and (opens refined etc., polymer material science and engineering, 2008,152).Butyl titanate can be provided
Quick cross-linking reacts, and can improve the cohesive of polymer, and can improve the heat-resisting quantity of phenolic resin to a certain extent
Can (Shi-hong Shen.et al, Polymer Degradation and Stability, 2013,514).There is research in phenol
More hydroquinones are introduced in urea formaldehyde, the structure containing compared with polyhydroxy can be obtained, but the hydroquinones newly added is more difficult complete
Portion and reactive modified phenolic resin.Increased with the modified phenolic resin cementability of hydroquinones, but the poor (Chunxia WANG of heat resistance
Deng forestry machinery and woodworking equipment, 2014,13).
There are problems that in above-mentioned method, due to the unicity of raw material, it is impossible to which satisfaction had both improved the resistance to of phenolic resin
It is hot, the cementability of phenolic resin is improved again.
The content of the invention
An object of the present invention, is to provide a kind of poly- titanium Borosiloxane of high temperature resistant simple to operate, excellent performance
(TiBSi) preparation method；There is provided a kind of cohesive force is strong, resistant to elevated temperatures modified phenolic resin adhesive for the second purpose.
The present invention is reacted at a lower temperature with polyborosiloxane, butyl titanate, acetylacetone,2,4-pentanedione and novolac first, is obtained
To the poly- titanium Borosiloxane containing a large amount of terminal hydroxy groups, itself there is good heat-resisting quantity；Then with this poly- titanium Borosiloxane
It is compound with phenolic resin, obtain modified phenolic resin adhesive.
The technical scheme is that：
The preparation method of poly- titanium Borosiloxane, it is characterised in that comprise the following steps：Poly- titanium Borosiloxane (TiBSi)
Prepare：It is first that novolac is admixed together in the presence of the solvent with butyl titanate chelate, then this mixture is added to
In polyborosiloxane, under nitrogen atmosphere, 60 DEG C of low-temp reaction 5h, water pump depressurizes 0.5~1h；Wherein butyl titanate chelate is
Butyl titanate is formed with acetylacetone,2,4-pentanedione equimolar than reaction, polyborosiloxane：The butyl titanate included in butyl titanate chelate：
Novolac mass ratio is 1:(0.2~0.6)：1.
Raw material polyborosiloxane, be MTES, MTMS, ethyl triethoxysilane,
Ethyl trimethoxy silane, vinyltrimethoxy silane, VTES, phenyltrimethoxysila,e, phenyl
One kind in triethoxysilane presses (1~2) with boric acid:1 molar ratio reaction is prepared and generated.It is preferred that with phenyl trimethoxy silicon
Alkane presses (1~2) with boric acid:1 mol ratio is reacted 3~5h at 140-150 DEG C and is prepared from, and number-average molecular weight is 800 or so.
Butyl titanate is mixed with acetylacetone,2,4-pentanedione equimolar ratio, is initially formed chelate, to reduce butyl titanate activity, after being easy to
The progress of continuous reaction.
Novolac preferably uses one in phenol, catechol, resorcinol, hydroquinones, phloroglucin, pyrogallol
Kind or it is several be prepared from formalin solution, number-average molecular weight be 600 or so.
The solvent be diethylene glycol dimethyl ether, dioxane, tetrahydrofuran, N, N '-dimethyl formamide it is any one
Kind.
It is excellent using the poly- titanium Borosiloxane of the present invention to the phenolic resin modified method for preparing modified phenolic resin adhesive
Choosing comprises the following steps：Poly- titanium Borosiloxane and base catalysis phenolic resin PF are pressed into (0.5~1):1 mass ratio is well mixed,
Obtain the synvaren that poly- titanium Borosiloxane is modified.
Above-mentioned base catalysis phenolic resin PF synthesis, preferably：With phenol and formaldehyde in molar ratio for 1:1.5, base catalyst
Consumption be the 6 ‰ of gross mass, reaction from 40 DEG C it is slow be warming up to 90 DEG C, be incubated 1.5 hours, then cool to 60~70 DEG C,
Water pump decompression steams water, obtains base catalysis phenolic resin PF.Described base catalyst is sodium hydroxide, potassium hydroxide, hydroxide
One kind in ammonium, sodium carbonate and barium hydroxide.
By modified phenolic resin adhesive through gluing, solidification, its carbon yield and adhesion strength are determined.
Effect of the present invention：
The present invention is reacted by polyborosiloxane, butyl titanate, acetylacetone,2,4-pentanedione, novolac, and synthesis contains a large amount of end hydroxyls
Base and the poly- titanium Borosiloxane (TiBSi) with excellent heat resistance；After being mixed with phenolic resin, its adhesive strength can be improved and resistance to
It is hot.Polycondensation reaction can occur with phenolic resin for substantial amounts of terminal hydroxy group in poly- titanium Borosiloxane during solidification, and wherein containing a large amount of
Silica, boron oxygen, titanyl structure, beneficial to its adhesion strength of raising and heat endurance.
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, relatively low to equipment requirement, gained
Poly- titanium Borosiloxane resistance to elevated temperatures is excellent, and containing substantial amounts of terminal hydroxy group, as modifying agent, the viscous of phenolic resin can be improved simultaneously
Knotting strength and heat-resisting quantity, a kind of feasible method is provided for the intensity and resistance to elevated temperatures of raising phenolic resin adhesive.
Embodiment
Poly- titanium Borosiloxane is made using polyborosiloxane, butyl titanate, acetylacetone,2,4-pentanedione, novolac as raw material in the present invention,
Then phenolic resin is modified, obtains higher and 800 DEG C higher compared with the carbon yield modified alkyd resin glue of adhesive strength and stick
Agent.
With reference to specific embodiment, the invention will be further described, but the protection of the present invention is not limited to embodiment
Involved scope.
Polyborosiloxane phenyltrimethoxysila,e presses (1~2) with boric acid:1 mol ratio 140-150 DEG C react 3~
5h is prepared from, and number-average molecular weight is 800 or so.
Fraction as described below is mass fraction.
Embodiment 1：
The preparation of poly- titanium Borosiloxane：Polyborosiloxane is (by phenyltrimethoxysila,e and boric acid in molar ratio 1:1,
Under nitrogen environment, reacted 3 hours in 150 DEG C, and deviate from solvent and be prepared from) 1 part of (being dissolved in 10 parts of tetrahydrofurans), fourth containing metatitanic acid
The chelate that 0.2 part of ester (is dissolved in 10 parts of tetrahydrofurans, butyl titanate and equimolar acetylacetone,2,4-pentanedione shape of the chelate by 0.2 part
Into), (phenol and formalin solution are prepared novolac under conditions of careless acid as catalyst, wherein phenol and formaldehyde mole
Than for 1:0.9) 1 part (being dissolved in 10 parts of tetrahydrofurans), three is admixed together, in a nitrogen atmosphere in 2h from room temperature progressively
60 DEG C are warming up to, 5h, water pump 0.5~1h of Depressor response is reacted, obtains poly- titanium Borosiloxane.
Embodiment 2:
The preparation of poly- titanium Borosiloxane：Polyborosiloxane is (by phenyltrimethoxysila,e and boric acid in molar ratio 1:1,
Under nitrogen environment, reacted 3 hours in 150 DEG C, and deviate from solvent and be prepared from) 1 part of (being dissolved in 10 parts of tetrahydrofurans), fourth containing metatitanic acid
The chelate that 0.4 part of ester (is dissolved in 10 parts of tetrahydrofurans, butyl titanate and equimolar acetylacetone,2,4-pentanedione shape of the chelate by 0.4 part
Into), (phenol and formalin solution are prepared novolac under conditions of careless acid as catalyst, wherein phenol and formaldehyde mole
Than for 1:0.9) 1 part (being dissolved in 10 parts of tetrahydrofurans), three is admixed together, in a nitrogen atmosphere in 2h from room temperature progressively
60 DEG C are warming up to, 5h, water pump 0.5~1h of Depressor response is reacted, obtains poly- titanium Borosiloxane.
Embodiment 3:
The preparation of poly- titanium Borosiloxane：Polyborosiloxane is (by phenyltrimethoxysila,e and boric acid in molar ratio 1:1,
Under nitrogen environment, reacted 3 hours in 150 DEG C, and deviate from solvent and be prepared from) 1 part of (being dissolved in 10 parts of tetrahydrofurans), fourth containing metatitanic acid
The chelate that 0.6 part of ester (is dissolved in 10 parts of tetrahydrofurans, butyl titanate and equimolar acetylacetone,2,4-pentanedione shape of the chelate by 0.6 part
Into), (phenol and formalin solution are prepared novolac under conditions of careless acid as catalyst, wherein phenol and formaldehyde mole
Than for 1:0.9) 1 part (being dissolved in 10 parts of tetrahydrofurans), three is admixed together, in a nitrogen atmosphere in 2h from room temperature progressively
60 DEG C are warming up to, 5h, water pump 0.5~1h of Depressor response is reacted, obtains poly- titanium Borosiloxane.
The molecular weight of poly- titanium Borosiloxane obtained by embodiment 1-3 and it is shown in Table 1 in 800 DEG C of carbon yield.Can from table
Go out, the number-average molecular weight of the poly- titanium Borosiloxane of gained is between 850~870 in embodiment 1~3,800 DEG C of carbon yield 71.40-
Between 71.69%, difference is little.
The molecular weight and carbon yield of poly- titanium Borosiloxane obtained by the embodiment 1-3 of table 1
Embodiment 4：
The synthesis of base catalysis phenolic resin：Using barium hydroxide as catalyst, by mass fraction for 43.6 parts phenol, 56.4
The formalin of part 36% and the mixing of 0.6 part of barium hydroxide, are slowly warming up to 90 DEG C by 40 DEG C, are incubated 1.5 hours, then drop
Temperature is to 60~70 DEG C, and water pump decompression steams the water of reaction generation, obtains base catalysis phenolic resin PF.
Embodiment 5：
The preparation and test of modified phenolic resin adhesive：With the 1 part of (weight of poly- titanium Borosiloxane obtained in embodiment 1
Part) and the phenolic resin 1 part (parts by weight) of embodiment 4 mixed, stir, take a part to be used as adhesive solidification, it is another
Part directly solidifies, and condition of cure is 150 DEG C, solidifies 4h.And contrasted with the self-curing of alkali phenolic resin adhesive.
Embodiment 6：
The preparation and test of modified phenolic resin adhesive：With the 1 part of (weight of poly- titanium Borosiloxane obtained in embodiment 1
Part) and the phenolic resin 2 parts (parts by weight) of embodiment 4 mixed, stir, take a part to be used as adhesive solidification, it is another
Part directly solidifies, and condition of cure is 150 DEG C, solidifies 4h.
Phenol-formaldehyde resin modified after solidifying obtained by embodiment 5-6, the solidification with the gained phenolic resin of embodiment 4 is contrasted, and is adopted
Its carbon yield and adhesion strength are determined with TGA and stretching, 2 are shown in Table.Modification of the phenolic resin adhesive Jing Guo poly- titanium Borosiloxane
Afterwards, adhesive strength is improved significantly, and 800 DEG C of Residual carbons also achieve certain raising.Work as TiBSi:PF (mass ratio)=
1:When 2, adhesive strength is up to 6.32MPa, and carbon yield is up to 70.18%.
| Numbering | TiBSi:PF (mass ratio) | Shear strength (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. a kind of preparation method of poly- titanium Borosiloxane (TiBSi), it is characterised in that comprise the following steps：First by novolac
It is admixed together in the presence of a solvent with butyl titanate chelate, then this mixture is added in polyborosiloxane,
Under nitrogen atmosphere, 60 DEG C of low-temp reaction 5h, water pump depressurizes 0.5~1h；Wherein butyl titanate chelate is butyl titanate and second
Acyl acetone equimolar is formed than reaction, polyborosiloxane：The butyl titanate included in butyl titanate chelate：Novolac quality
Than for 1:(0.2~0.6)：1.
2. it is MTES, methyl three according to the method for claim 1, it is characterised in that raw material polyborosiloxane
Methoxy silane, ethyl triethoxysilane, ethyl trimethoxy silane, vinyltrimethoxy silane, the ethoxy of vinyl three
One kind in base silane, phenyltrimethoxysila,e, phenyl triethoxysilane presses (1~2) with boric acid:1 molar ratio reaction system
It is standby and generate.
3. according to the method for claim 1, it is characterised in that novolac phenol, catechol, resorcinol, to benzene two
Phenol, phloroglucin, pyrogallol are a kind of or several are prepared from formalin solution.
4. according to the method for claim 1, it is characterised in that the solvent is diethylene glycol dimethyl ether, dioxane, tetrahydrochysene furan
Mutter, N, N '-dimethyl formamide any one.
5. the poly- titanium Borosiloxane (TiBSi) prepared using the method for claim 1 the method heat resistance modified to phenolic resin, its
It is characterised by, comprises the following steps：Poly- titanium Borosiloxane and base catalysis phenolic resin PF are taken by (0.5~1):1 mass ratio is mixed
Close uniform, obtain poly- titanium Borosiloxane modified phenolic resin adhesive.
6. according to the method for claim 5, it is characterised in that poly- titanium Borosiloxane and base catalysis phenolic resin PF mass ratio 1:
1。
7. according to the method for claim 5, it is characterised in that base catalysis phenolic resin PF synthesis, massaged with phenol and formaldehyde
You are than being 1:1.5, the consumption of base catalyst is the 6 ‰ of gross mass, and reaction is slowly warming up to 90 DEG C from 40 DEG C, is incubated 1.5 hours,
Then 60~70 DEG C are cooled to, water pump decompression steams water, obtains base catalysis phenolic resin PF.
8. according to the method for claim 7, it is characterised in that described base catalyst is sodium hydroxide, potassium hydroxide, hydroxide
One kind in ammonium, sodium carbonate and barium hydroxide.
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