CN103467745B - The preparation method of terminal alkoxy polysiloxane - Google Patents
The preparation method of terminal alkoxy polysiloxane Download PDFInfo
- Publication number
- CN103467745B CN103467745B CN201310395394.0A CN201310395394A CN103467745B CN 103467745 B CN103467745 B CN 103467745B CN 201310395394 A CN201310395394 A CN 201310395394A CN 103467745 B CN103467745 B CN 103467745B
- Authority
- CN
- China
- Prior art keywords
- silane
- component
- polysiloxane
- preparation
- terminal alkoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 49
- -1 polysiloxane Polymers 0.000 title claims abstract description 46
- 125000003545 alkoxy group Chemical group 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 230000029936 alkylation Effects 0.000 claims abstract description 3
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- KGNDVXPHQJMHLX-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)cyclohexanamine Chemical compound CO[Si](OC)(OC)CCCNC1CCCCC1 KGNDVXPHQJMHLX-UHFFFAOYSA-N 0.000 claims description 5
- CQERQNNEKFKVFU-UHFFFAOYSA-N triethoxy(3-piperazin-1-ylpropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCNCC1 CQERQNNEKFKVFU-UHFFFAOYSA-N 0.000 claims description 5
- VKNRMUNOBKFFMA-UHFFFAOYSA-N triethoxy(3-piperidin-1-ylpropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCCCC1 VKNRMUNOBKFFMA-UHFFFAOYSA-N 0.000 claims description 5
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 claims description 4
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical compound CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 claims description 4
- TYSBVDFCBCSRFS-UHFFFAOYSA-N dimethoxy-(morpholin-4-ylmethoxy)-propylsilane Chemical compound O1CCN(CC1)CO[Si](OC)(OC)CCC TYSBVDFCBCSRFS-UHFFFAOYSA-N 0.000 claims description 4
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 4
- LENYMJLFWIMHEP-UHFFFAOYSA-N triethoxy(3-pyrrolidin-1-ylpropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCCC1 LENYMJLFWIMHEP-UHFFFAOYSA-N 0.000 claims description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 4
- RYINGNAZWSKAII-UHFFFAOYSA-N triethoxy-[3-(1h-imidazol-2-yl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCC1=NC=CN1 RYINGNAZWSKAII-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- LNVWGBOMPSRZFG-UHFFFAOYSA-N 3-(1h-imidazol-2-yl)propyl-trimethoxysilane Chemical compound CO[Si](OC)(OC)CCCC1=NC=CN1 LNVWGBOMPSRZFG-UHFFFAOYSA-N 0.000 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 2
- PWNWVFIHKVNTLV-UHFFFAOYSA-N N1(CCOCC1)CCO[Si](OCC)(OCC)CCC Chemical compound N1(CCOCC1)CCO[Si](OCC)(OCC)CCC PWNWVFIHKVNTLV-UHFFFAOYSA-N 0.000 claims description 2
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 claims description 2
- YFBFAHMPVMWKIM-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)cyclohexanamine Chemical compound CCO[Si](OCC)(OCC)CCCNC1CCCCC1 YFBFAHMPVMWKIM-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 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
- HXYMWKLNCJPAKW-UHFFFAOYSA-N trimethoxy(3-piperazin-1-ylpropyl)silane Chemical compound CO[Si](OC)(OC)CCCN1CCNCC1 HXYMWKLNCJPAKW-UHFFFAOYSA-N 0.000 claims description 2
- PUFJKMYZVNKQCV-UHFFFAOYSA-N trimethoxy(3-piperidin-1-ylpropyl)silane Chemical compound CO[Si](OC)(OC)CCCN1CCCCC1 PUFJKMYZVNKQCV-UHFFFAOYSA-N 0.000 claims description 2
- NGLLPRYTJGRGEU-UHFFFAOYSA-N trimethoxy(3-pyrrolidin-1-ylpropyl)silane Chemical compound CO[Si](OC)(OC)CCCN1CCCC1 NGLLPRYTJGRGEU-UHFFFAOYSA-N 0.000 claims description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 2
- 229940094989 trimethylsilane Drugs 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- ISWQCIVKKSOKNN-UHFFFAOYSA-L Tiron Chemical compound [Na+].[Na+].OC1=CC(S([O-])(=O)=O)=CC(S([O-])(=O)=O)=C1O ISWQCIVKKSOKNN-UHFFFAOYSA-L 0.000 description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 7
- 238000001311 chemical methods and process Methods 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a kind of preparation method of terminal alkoxy polysiloxane, comprise the following steps: step one: batching: component A: hydroxy-end capped polysiloxane; B component: organoalkoxysilane/or its partial hydrolystate with at least 3 alkoxyl groups; Component C: the organoalkoxysilane of ammonia alkyl; Step 2: component A, B, C are added in high speed dispersor, under rare gas element or vacuum, high-speed stirring; Step 3: material step 2 stirred is under rare gas element or vacuum, and temperature is 0 ~ 100 DEG C, places 0.5 ~ 24h, carries out terminal alkylations original position end capping, obtain terminal alkoxy polysiloxane.This preparation method adopts the organoalkoxysilane of ammonia alkyl as catalyzer, the polysiloxane that catalysis is hydroxy-end capped and organoalkoxysilane original position end-blocking, prepared terminal alkoxy polysiloxane viscosity B coefficent is little, and side reaction is few, and technique is simple, be easy to control, easy to operate, energy consumption is little.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of preparation method of terminal alkoxy polysiloxane.
Background technology
When terminal alkoxy polysiloxane meets moisture, alkoxyl group hydrolyzable, and then crosslinked polymer is solidified.Only discharging tasteless, neutral low molecule alcohols material in solidification process, to had no corrosive effect on metals such as copper, lead, zinc, is a kind of environmentally friendly macromolecular material.The dealcoholized type room temperature vulcanized silicone rubber product that based on it prepared by polymkeric substance, can can keep good physicals and electrical property in the environment of harshness, be widely used in the industries such as building, automobile, electric power, new forms of energy, electronic apparatus and fix as bonding, sealing, encapsulation, coating, components and parts.
The hydrolytic activity of neutral alcoxyl fundamental mode silane is very low, and has after hydroxy-terminated polysiloxane mix, very difficultly effectively forms terminal alkoxy polysiloxane.US3161614 discloses in anhydrous conditions, and hydroxy-terminated polysiloxane and chloride organoalkoxysilane react, and adds pyridine solvent as hydrogenchloride receptor, generates high boiling pyridine hydrochloride, with in reaching and the object of hydrogenchloride.Along with the development of closed-end technology, terminal alkoxy polysiloxane selects hydroxy-end capped polysiloxane and organoalkoxysilane original position end capping under certain catalysts conditions to obtain usually.Domestic and international patent and document mainly concentrate on the selection of catalyzer, and the mixture of US3542901 report organic amine compound, US3161614 carboxylic metallic salt and amine, EP070786 hydroxylamine derivative, US5352751 adopt alkali metal hydroxide, EP0564253 organolithium, CN1264404 Bronsted acid or the catalyzer such as Lewis acid, CN1283212 phosphate ester acid to there is lower catalysis alkoxyl group original position end capping.After end-blocking is ended, the acid that needs are corresponding or alkali make catalyst deactivation.In order to ensure the package stability of the finished product, the amount of deactivator must be accurately consistent with the amount of catalyzer, and during concrete end-blocking, often need use excessive deactivator.Because deactivator has higher equilibrium activity, so again must remove from product.Therefore, select a kind of suitable catalyzer, additionally do not add deactivator, just make terminal alkoxy polysiloxane have good storage stability, have very important significance.
Summary of the invention
The object of the invention is the preparation method that a kind of terminal alkoxy polysiloxane is provided for the deficiencies in the prior art, be characterized in the polysiloxane that the organoalkoxysilane catalysis of employing ammonia hydrocarbyl functional is hydroxy-end capped and organoalkoxysilane original position end-blocking.
In order to reach above-mentioned technique effect, the present invention takes following technical scheme:
A preparation method for terminal alkoxy polysiloxane, comprises the following steps:
Step one: batching: component A: hydroxy-end capped polysiloxane; B component: organoalkoxysilane/or its partial hydrolystate with at least 3 alkoxyl groups; Component C: the organoalkoxysilane with the ammonia alkyl of general formula [I],
general formula [I],
Wherein: R
1for having the alkyl of 1 ~ 8 carbon atom;
R
2for having the alkyl of 1 ~ 8 carbon atom;
R
3for hydrogen or alkyl or the-OR with 1 ~ 2 carbon atom
1or-OR
2group;
X is 0 or 1;
Step 2: component A, B, C are added in high speed dispersor, under rare gas element or vacuum (vacuum tightness is 0.08 ~ 0.099MPa), high-speed stirring;
Step 3: material step 2 stirred is under rare gas element or vacuum, and temperature is 0 ~ 100 DEG C, places 0.5 ~ 24h, carries out terminal alkylations original position end capping, obtain terminal alkoxy polysiloxane.
In above-mentioned preparation method, described component A preferably has the linear α of general formula [II], alpha, omega-dihydroxy polysiloxane:
HO-[R
2siO]
n-H, general formula [II],
Wherein: R is the alkyl with 1 ~ 8 carbon atom; N has certain value, and it is 100 ~ 150000mPaS that this value corresponds to the hydroxy-end capped viscosity of polysiloxane when temperature 25 DEG C, and namely the viscosity of component A when temperature 25 DEG C is that 100 ~ 150000mPaS all can be used in the present invention.In the application of reality, in component A the value of n be all adopt first measure viscosity and R group after backstepping obtain the value of n.
In above-mentioned preparation method, described B component has the structural formula of general formula [III]:
R
4 msi (OR
5)
4-m, general formula [III],
Wherein: R
4for having alkyl or the aryl of 1 ~ 8 carbon atom; R
5for having the alkyl of 1 ~ 8 carbon atom; M is 0 or 1.
Be more specifically: described B component is at least one in methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, methyl three butoxy silane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, ethyl trimethoxy silane, ethyl triethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane.
According to a preferred embodiment of the invention, described B component is at least one in tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, vinyltrimethoxy silane, vinyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane.
In above-mentioned preparation method, described component C has the structural formula of general formula [IV] or [V]:
general formula [IV];
general formula [V];
Wherein: R
1for having the alkyl of 1 ~ 8 carbon atom;
R
2for having the alkyl of 1 ~ 8 carbon atom;
R
3for alkyl or the-OR of hydrogen or 1 ~ 2 carbon atom
1or-OR
2group;
R
6for hydrogen or have the alkyl of 2 ~ 10 carbon atoms, aryl or aryl;
R
7for hydrogen or have the alkyl of 2 ~ 10 carbon atoms, aryl or aryl;
R
8for in the alkyl with 2 ~ 10 carbon atoms or the hydrocarbyl chain with 2 ~ 10 carbon atoms containing NH, O, H group;
X is 0 or 1.
Be more specifically: described component C is γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxy diethoxy silane, N-cyclohexyl-γ-aminopropyltrimethoxysilane, N-cyclohexyl-γ-aminopropyl triethoxysilane, diethylin oxypropyl trimethyl silane, diethylin propyl-triethoxysilicane, aniline propyl trimethoxy silicane, imidazolylpropyl Trimethoxy silane, imidazolylpropyl triethoxyl silane, piperidinylpropyl Trimethoxy silane, piperidinylpropyl triethoxyl silane, piperazinopropyl Trimethoxy silane, piperazinopropyl triethoxyl silane, morpholinyl propyl Trimethoxy silane, morpholinyl propyl triethoxyl silane, pyrrolidinylpropyl Trimethoxy silane, at least one in pyrrolidinylpropyl triethoxyl silane.
As the preferred embodiments of the present invention, preferably: described component C is at least one in γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-cyclohexyl-γ-aminopropyltrimethoxysilane, imidazolylpropyl triethoxyl silane, piperidinylpropyl triethoxyl silane, piperazinopropyl triethoxyl silane, morpholinyl propyl Trimethoxy silane, pyrrolidinylpropyl triethoxyl silane.
In above-mentioned preparation method, the mass ratio of described component A, B component, component C is 100:(0.5 ~ 10): (0.01 ~ 10).
As the preferred embodiments of the present invention, preferably: the mass ratio of described component A, B component, component C is 100:(1 ~ 8): (0.1 ~ 6).
In above-mentioned preparation method, the rotating speed stirred in step 2 is 200 ~ 3000r/min, and churning time is 1 ~ 30min.
As the preferred embodiments of the present invention, preferably: in step 3, temperature is 20 ~ 60 DEG C, storage period is 1 ~ 12h.
The present invention compared with prior art, has following beneficial effect:
(1) this preparation method adopts the organoalkoxysilane of ammonia alkyl as catalyzer, the polysiloxane that catalysis is hydroxy-end capped and organoalkoxysilane original position end-blocking, without the need to being removed by catalyzer after having reacted, reduces the operation steps of preparation method.
(2) the terminal alkoxy polysiloxane viscosity B coefficent prepared by the method is little, and side reaction is few, and technique is simple, be easy to control, easy to operate, energy consumption is little, can be widely used in that single-component de-alcoholized room temperature vulcanized organosilicon sealing material is full-automatic to be produced greatly.
(3) after this preparation method only needs each component fully to mix, at 0 ~ 100 DEG C, can react obtained terminal alkoxy polysiloxane, reaction conditions is easy to control, and operation steps is simple.
Accompanying drawing explanation
The hydroxy-end capped polysiloxane that Fig. 1 adopts for embodiment 1
1h NMR schemes.
Fig. 2 is the terminal alkoxy polysiloxane that obtains of embodiment 1
1h NMR schemes.
Embodiment
Below in conjunction with embodiments of the invention, the invention will be further elaborated.
The performance test of terminal alkoxy polysiloxane prepared by embodiments of the invention:
1) organopolysiloxane viscosity is tested by GB/T10247-2008;
2) by quick tiron chemical process, inspection end-blocking effect;
3) by JY/T007-1996 superconducting pulse Fourier transform nuclear magnetic resonance spectral method general rule, polysiloxane end-functionalization situation is characterized.
Embodiment 1:
In high speed dispersor, add the α of 100 mass parts viscosity (25 DEG C) 650mPas being cooled to room temperature through 100 DEG C of decompression dehydration 3h, alpha, omega-dihydroxy polydimethyl siloxane, its proton nmr spectra (
1h NMR) see accompanying drawing 1.Add 4 mass parts methyltrimethoxy silanes, 2 mass parts vinyltrimethoxy silanes, after mixing, institute's viscosimetric is 473mPas; Add 1 mass parts γ-aminopropyltrimethoxysilane, 2 mass parts N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, under protection of inert gas, with 2000r/min high-speed stirring 2min.2h is placed in lower 50 DEG C of protection of inert gas, by quick tiron chemical process inspection end-blocking situation, without viscosity peak phenomenon.The viscosity of gained terminal alkoxy polysiloxane is 478mPas, its
1hNMR is shown in accompanying drawing 2.Continue placement under protection of inert gas 30 days, institute's viscosimetric is 482mPas.
1h NMR analyzes, α, and alpha, omega-dihydroxy polydimethyl siloxane, after end alkoxy group, disappears at the silicone hydroxyl peak at δ=1.9ppm place, occurs alcoxyl base peak at δ=3.6ppm place.
Embodiment 2:
In high speed dispersor, add the α of 600 mass parts viscosity (25 DEG C) 17700mPas being cooled to room temperature through 100 DEG C of decompression dehydration 3h, the α of alpha, omega-dihydroxy polydimethyl siloxane and 60 mass parts viscosity (25 DEG C) 150000mPas, alpha, omega-dihydroxy polydimethyl siloxane, 24 mass parts tetraethoxysilanes, 6 mass parts phenyltrimethoxysila,e are added after dispersed, after mixing, institute's viscosimetric is 18600mPas; Add 4 mass parts N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, 5 mass parts imidazolylpropyl triethoxyl silanes, under keeping vacuum tightness 0.08 ~ 0.099MPa condition, with 1500r/min high-speed stirring 5min.Keep vacuum tightness 0.08 ~ 0.099MPa, at 30 DEG C, place 4h, by quick tiron chemical process inspection end-blocking situation, without viscosity peak phenomenon.The viscosity of gained terminal alkoxy polysiloxane is 19400mPas.Continue placement under protection of inert gas 30 days, institute's viscosimetric is 19700mPas.Warp
1h NMR analyzes, not containing silicone hydroxyl.
Embodiment 3:
In high speed dispersor, add the α of 1000 mass parts viscosity (25 DEG C) 49500mPas, alpha, omega-dihydroxy polydimethyl siloxane, 10 mass parts vinyltrimethoxy silanes, 30 mass parts Union carbide A-162s, after mixing, institute's viscosimetric is 42800mPas; Add 1 mass parts N-cyclohexyl-γ-aminopropyltrimethoxysilane, 2 mass parts piperidinylpropyl triethoxyl silanes, 2 mass parts piperazinopropyl triethoxyl silanes, under protection of inert gas, with 800r/min high-speed stirring 15min.Under protection of inert gas, place 6h in 25 DEG C, by quick tiron chemical process inspection end-blocking situation, without viscosity peak phenomenon.The viscosity of gained terminal alkoxy polysiloxane is 47700mPas.Continue placement under protection of inert gas 30 days, institute's viscosimetric is 47900mPas.Warp
1h NMR analyzes, not containing silicone hydroxyl.
Embodiment 4:
In high speed dispersor, add the α of 3000 mass parts viscosity (25 DEG C) 78900mPas, the α of alpha, omega-dihydroxy polydimethyl siloxane and 30 mass parts viscosity (25 DEG C) 100mPas, alpha, omega-dihydroxy polydimethyl siloxane, 45 mass parts vinyltriethoxysilanes, 30 mass parts phenyl triethoxysilanes, 15 mass parts tetraethoxysilanes are added after dispersed, after mixing, institute's viscosimetric is 71200mPas; Add 5 mass parts morpholinyl propyl Trimethoxy silanes, 4 mass parts pyrrolidinylpropyl triethoxyl silanes, under protection of inert gas, with 400r/min high-speed stirring 25min.Under protection of inert gas, place 8h in 40 DEG C, by quick tiron chemical process inspection end-blocking situation, without viscosity peak phenomenon.The viscosity of gained terminal alkoxy polysiloxane is 76500mPas.Continue placement under protection of inert gas 30 days, institute's viscosimetric is 77100mPas.Warp
1h NMR analyzes, not containing silicone hydroxyl.
Comparative example 1:
Do not add γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, repeat embodiment 1.Place 30 days under protection of inert gas, add quick tiron, occur obvious viscosity peak phenomenon immediately.
Comparative example 2:
Add 2.5 mass parts dibutylamine and replace N-cyclohexyl-γ-aminopropyltrimethoxysilane, piperidinylpropyl triethoxyl silane, piperazinopropyl triethoxyl silane, repeat embodiment 3, by quick tiron chemical process inspection end-blocking situation, without viscosity peak phenomenon.The viscosity of gained terminal alkoxy polysiloxane is 49500mPas.Continue placement under protection of inert gas 30 days, institute's viscosimetric is 57900mPas, and viscosity B coefficent is more than 10%.
Although with reference to explanatory embodiment of the present invention, invention has been described here, above-described embodiment is only the present invention's preferably embodiment, embodiments of the present invention are not restricted to the described embodiments, should be appreciated that, those skilled in the art can design a lot of other amendment and embodiment, these amendments and embodiment will drop within spirit disclosed in the present application and spirit.
Claims (6)
1. a preparation method for terminal alkoxy polysiloxane, is characterized in that comprising the following steps:
Step one: batching: component A: hydroxy-end capped polysiloxane, B component: organoalkoxysilane/or its partial hydrolystate with at least 3 alkoxyl groups, component C: γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxy diethoxy silane, N-cyclohexyl-γ-aminopropyltrimethoxysilane, N-cyclohexyl-γ-aminopropyl triethoxysilane, diethylin oxypropyl trimethyl silane, diethylin propyl-triethoxysilicane, aniline propyl trimethoxy silicane, imidazolylpropyl Trimethoxy silane, imidazolylpropyl triethoxyl silane, piperidinylpropyl Trimethoxy silane, piperidinylpropyl triethoxyl silane, piperazinopropyl Trimethoxy silane, piperazinopropyl triethoxyl silane, morpholinyl propyl Trimethoxy silane, morpholinyl propyl triethoxyl silane, pyrrolidinylpropyl Trimethoxy silane, at least one in pyrrolidinylpropyl triethoxyl silane,
Step 2: component A, B, C are added in high speed dispersor, under rare gas element or vacuum, high-speed stirring;
Step 3: material step 2 stirred is under rare gas element or vacuum, and temperature is 0 ~ 100 DEG C, places 0.5 ~ 24h, carries out terminal alkylations original position end capping, obtain terminal alkoxy polysiloxane.
2. the preparation method of terminal alkoxy polysiloxane according to claim 1, is characterized in that described component A is for having the linear α of general formula [II], alpha, omega-dihydroxy polysiloxane:
HO-[R
2siO]
n-H, general formula [II],
Wherein: R is the alkyl with 1 ~ 8 carbon atom; N has certain value, and it is 100 ~ 150000mPaS that this value corresponds to the hydroxy-end capped viscosity of polysiloxane when temperature 25 DEG C.
3. the preparation method of terminal alkoxy polysiloxane according to claim 1, is characterized in that described B component has the structural formula of general formula [III]:
R
4 msi (OR
5)
4-m, general formula [III],
Wherein: R
4for having alkyl or the aryl of 1 ~ 8 carbon atom; R
5for having the alkyl of 1 ~ 8 carbon atom; M is 0 or 1.
4. the preparation method of terminal alkoxy polysiloxane according to claim 3, is characterized in that described B component is at least one in methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, methyl three butoxy silane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, ethyl trimethoxy silane, ethyl triethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane.
5. the preparation method of terminal alkoxy polysiloxane according to claim 1, is characterized in that the mass ratio of described component A, B component, component C is 100:(0.5 ~ 10): (0.01 ~ 10).
6. the preparation method of terminal alkoxy polysiloxane according to claim 1, it is characterized in that the rotating speed stirred in step 2 is 200 ~ 3000r/min, churning time is 1 ~ 30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310395394.0A CN103467745B (en) | 2013-09-03 | 2013-09-03 | The preparation method of terminal alkoxy polysiloxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310395394.0A CN103467745B (en) | 2013-09-03 | 2013-09-03 | The preparation method of terminal alkoxy polysiloxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103467745A CN103467745A (en) | 2013-12-25 |
| CN103467745B true CN103467745B (en) | 2015-08-05 |
Family
ID=49792801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310395394.0A Active CN103467745B (en) | 2013-09-03 | 2013-09-03 | The preparation method of terminal alkoxy polysiloxane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103467745B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519246A (en) * | 2016-11-21 | 2017-03-22 | 成都硅宝科技股份有限公司 | Polyalkyloxy-terminated polysiloxane and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674524A (en) * | 2016-12-30 | 2017-05-17 | 广州盛泰诺新材料科技有限公司 | Preparation method of alkoxy-terminated polydimethylsiloxane |
| CN106823991A (en) * | 2017-01-06 | 2017-06-13 | 广州市景琛高新科技有限公司 | A kind of cationic surfactant and preparation method thereof |
| JP7375044B2 (en) * | 2019-05-06 | 2023-11-07 | ワッカー ケミー アクチエンゲゼルシャフト | Method for preparing polyorganosiloxane |
| CN113307975A (en) * | 2020-12-30 | 2021-08-27 | 佛山市南海区波尔有机硅有限公司 | Alkoxy-terminated polysiloxane and preparation method thereof |
| CN115505126B (en) * | 2022-07-08 | 2023-06-06 | 橙天新材料(广州)有限公司 | Preparation method of beta-end siloxane-based polydimethylsiloxane |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202506A (en) * | 1997-06-17 | 1998-12-23 | 希尔斯硅股份有限公司 | Alkoxy crosslinked RTV1 silastic mixture |
| CN1255514A (en) * | 1998-12-02 | 2000-06-07 | 瓦克化学有限公司 | Organic polyorganosiloxane compsn. for making elastomer through removing alcohol and cross linking |
| CN1264404A (en) * | 1997-07-31 | 2000-08-23 | 瓦克化学有限公司 | Cross-linkable organopolysiloxane meterials formed into elastomers by separating alcohols |
| CN1283212A (en) * | 1997-12-22 | 2001-02-07 | 瓦克化学有限公司 | Organopolysiloxane materials which can be cross-linked by cleaving alcohols into elastomers |
| CN1637073A (en) * | 2003-09-17 | 2005-07-13 | 信越化学工业株式会社 | Organopolysiloxane composition and electronic part encapsulated therewith |
| CN101497696A (en) * | 2008-12-09 | 2009-08-05 | 张家港科道化学有限公司 | Alpha, alpha', omega, omega'-tetraalkoxy amino modified polysiloxane, preparation and use thereof |
| CN101517009A (en) * | 2006-09-18 | 2009-08-26 | 陶氏康宁公司 | Fillers, pigments and mineral powders treated with organopolysiloxanes |
| CN101671958A (en) * | 2009-10-13 | 2010-03-17 | 辽宁恒星精细化工（集团）有限公司 | Polysiloxane crease resistant finishing agent composition for natural fiber and preparation method thereof |
| CN101787211A (en) * | 2009-12-31 | 2010-07-28 | 深圳市钧泰丰新材料有限公司 | High-transparency and high-strength room temperature vulcanization organosilicon electron pouring sealant and preparation method and application thereof |
-
2013
- 2013-09-03 CN CN201310395394.0A patent/CN103467745B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202506A (en) * | 1997-06-17 | 1998-12-23 | 希尔斯硅股份有限公司 | Alkoxy crosslinked RTV1 silastic mixture |
| CN1264404A (en) * | 1997-07-31 | 2000-08-23 | 瓦克化学有限公司 | Cross-linkable organopolysiloxane meterials formed into elastomers by separating alcohols |
| CN1283212A (en) * | 1997-12-22 | 2001-02-07 | 瓦克化学有限公司 | Organopolysiloxane materials which can be cross-linked by cleaving alcohols into elastomers |
| CN1255514A (en) * | 1998-12-02 | 2000-06-07 | 瓦克化学有限公司 | Organic polyorganosiloxane compsn. for making elastomer through removing alcohol and cross linking |
| CN1637073A (en) * | 2003-09-17 | 2005-07-13 | 信越化学工业株式会社 | Organopolysiloxane composition and electronic part encapsulated therewith |
| CN101517009A (en) * | 2006-09-18 | 2009-08-26 | 陶氏康宁公司 | Fillers, pigments and mineral powders treated with organopolysiloxanes |
| CN101497696A (en) * | 2008-12-09 | 2009-08-05 | 张家港科道化学有限公司 | Alpha, alpha', omega, omega'-tetraalkoxy amino modified polysiloxane, preparation and use thereof |
| CN101671958A (en) * | 2009-10-13 | 2010-03-17 | 辽宁恒星精细化工（集团）有限公司 | Polysiloxane crease resistant finishing agent composition for natural fiber and preparation method thereof |
| CN101787211A (en) * | 2009-12-31 | 2010-07-28 | 深圳市钧泰丰新材料有限公司 | High-transparency and high-strength room temperature vulcanization organosilicon electron pouring sealant and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519246A (en) * | 2016-11-21 | 2017-03-22 | 成都硅宝科技股份有限公司 | Polyalkyloxy-terminated polysiloxane and preparation method thereof |
| CN106519246B (en) * | 2016-11-21 | 2022-03-25 | 成都硅宝科技股份有限公司 | Polyalkoxy-terminated polysiloxanes and method for the production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103467745A (en) | 2013-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103467745B (en) | The preparation method of terminal alkoxy polysiloxane | |
| CN107286897B (en) | Single-component low-viscosity dealcoholized organic silicon pouring sealant and preparation method thereof | |
| CN102585504B (en) | Moisture-thickening heat-conductive silicone grease composition | |
| CN103087556B (en) | Surface treatment method and application of heat-conducting filler | |
| CN103709988B (en) | Silica gel for electronic components and preparation method thereof | |
| CN102532907B (en) | Preparation method of oil-resistant room temperature vulcanization deoximation silicon rubber | |
| CN104558612B (en) | A kind of alkoxy end-capped polysiloxane polymer and preparation method thereof | |
| JP5905125B2 (en) | Method for producing polysilsesquioxane using carbon dioxide solvent and polysilsesquioxane | |
| CN101200594A (en) | Monocomponent dealcoholized cold curing silicon rubber | |
| CN102093721B (en) | Single-component alcohol/ketoxime-removed room temperature vulcanizing silicone rubber and preparation method thereof | |
| CN107312495A (en) | A kind of tack high-temperature silicon disulfide rubber band and preparation method thereof | |
| CN104877139A (en) | Tackifier for LED packaging adhesive and preparation method of tackifier | |
| Zhao et al. | Preparation and characterization of room temperature vulcanized silicone rubber using α-amine ketoximesilanes as auto-catalyzed cross-linkers | |
| CN102952403A (en) | Additive organosilicon heat-conducting electronic potting adhesive and manufacturing method thereof | |
| CN103087320B (en) | Preparation method of hydroxyl-terminated polymethylphenyl silicone oil | |
| CN104497959B (en) | Single-component room-temperature-vulsilicone silicone rubber sealant and preparation method thereof | |
| CN105153419A (en) | Heat-curable resin composition | |
| CN104558611B (en) | A kind of MDTQ silicones and its preparation method and application | |
| CN109749453A (en) | Titanate esters catalyst composition and its preparation method and application | |
| CN102952270A (en) | Polysiloxane polymer and preparation method thereof, as well as single-component dealcoholized silicon rubber and preparation method thereof | |
| CN104927058B (en) | Hydroxyl polysiloxane end-capping modification method | |
| CN111440323A (en) | Synthesis method of alkoxy-terminated organic silicon polyether copolymer and preparation of sealant thereof | |
| CN115895267A (en) | Dual-curing organosilicon polymer-benzoxazine-epoxy resin hybrid encapsulation material and preparation method thereof | |
| CN109439274B (en) | Preparation method of oil-resistant sealant | |
| CN106867024A (en) | A kind of Abietyl modified organosilane cross-linking agent of dealcoholized type room temperature vulcanized silicone rubber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |