CN106366278A - Synthesis method of alpha type silane terminated polyurethane - Google Patents
Synthesis method of alpha type silane terminated polyurethane Download PDFInfo
- Publication number
- CN106366278A CN106366278A CN201610765481.4A CN201610765481A CN106366278A CN 106366278 A CN106366278 A CN 106366278A CN 201610765481 A CN201610765481 A CN 201610765481A CN 106366278 A CN106366278 A CN 106366278A
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- CN
- China
- Prior art keywords
- end capped
- silane
- hydroxyl
- type silane
- synthetic method
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invnetioon provides a synthesis method of alpha type silane terminated polyurethane. The synthesis method comprises the following steps: selecting hydroxyl terminated polyether glycol with a proper molecular weight, adding a -NCO containing compound, heating to 60 to 130 DEG C under the action of a catalyst for reaction for 60 to 180 minutes, adding alpha type amino silane, and heating to 60 to 130 DEG C for reaction for 60 to 180 minutes, so as to finally obtain silane terminated polyurethane, wherein the structure of the alpha type amino silane is R1NHCH2Si(OR)3, wherein R1 is phenyl, ethyl or propyl, and R is methoxyl or ethyoxyl. The synthesis method avoids introduction of isocyanate silane which is high in cost and inconvenient to produce; by the two reaction steps, hydroxyl on a polyether molecular chain can be eliminated more thoroughly; the existence of the hydroxyl is unfavorable for the stability of a later formula.
Description
Technical field
The invention belongs to the synthesis technical field of chemical products, particularly to the synthetic method of α type silane end capped polyurethane.
Background technology
Produce in the market silane end capped polyurethane method have multiple, however it is necessary that it is high and produce not to introduce price
Convenient isocyanato silanes, and the hydroxyl on the pfpe molecule chain in reactions steps cannot eliminate thoroughly, and hydroxyl
Presence unfavorable to the stability of later stage formula.
Content of the invention
Goal of the invention: the technical problem to be solved is the synthetic method providing α type silane end capped polyurethane.
Technical scheme: the present invention provides the synthetic method of α type silane end capped polyurethane, comprises the following steps: it is suitable to select
The hydroxy-end capped polyether polyol of molecular weight, adds the compound containing-nco, in the presence of catalyst, it is heated to 60～
130 DEG C carry out reacting 60～180 minutes, are subsequently adding α type amino silane, are heated to 60～130 DEG C and carry out reacting 60～180 points
Clock, finally gives Silante terminated polyurethane；The structure of described α type amino silane is r1nhch2si(or)3, wherein, r1For benzene
Base, ethyl, propyl group；R is methoxyl group or ethyoxyl.
Synthetic reaction formula is specific as follows:
～～～～-oh+nco-r-nco →～～～～-nchoo-r-nco
～～～～-nchoo-r-nco+r1nhch2si(or)3→～～～～-nchoo-r-nhconh r1ch2si
(or)3.
Wherein, above-mentioned polyether polyol molecular weight is 3000～10000.
Wherein, while hydroxy-end capped or hydroxy-end capped in above-mentioned polyether polyol, side chain also contains hydroxyl.
Wherein, the above-mentioned compound containing-nco is one of tdi, mdi or hdi.
Wherein, the hydroxyl of above-mentioned polyether polyol and the mol ratio of-nco of compound containing-nco are 2:1～1:2.
Wherein, above-mentioned catalyst is organic titanium.
Present invention additionally comprises the α type silane end capped polyurethane of above-mentioned legal manner synthesis.
Present invention additionally comprises application in terms of preparation chemical products for the above-mentioned α type silane end capped polyurethane.
Beneficial effect: with respect to prior art, the present invention possesses advantages below:
1st, the isocyanato silanes introduced high price and produce inconvenience are avoided；
2nd, two-step reaction is more thorough to the hydroxyl eliminating on pfpe molecule chain, and the presence of hydroxyl is stablized to later stage formula
Property is unfavorable.
3rd, without the addition environmentally harmful catalyst such as organotin or Organic leadP in reactions steps of the present invention；Therefore this is anti-
Response environment does not pollute, and belongs to environmentally friendly chemical reaction.
4th, after the polymer that obtains of present invention reaction carries out performance test after passing through addition MTMS, each side
The performance in face is superior to the product bought on the market.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, it is as it will be easily appreciated by one skilled in the art that real
Apply the specific material proportion described by example, process conditions and its result and be merely to illustrate the present invention, and should not also will not limit
The present invention described in detail in claims processed.
Embodiment 1
Choose poly(propylene oxide) ppg8000 that end is hydroxyl, reaction bulb adds 200 grams of this polyether polyol, so
Add 8.7 grams of toluene di-isocyanate(TDI) (tdi) afterwards, add catalyst organic titanium, react 60 minutes at 90 DEG C, be subsequently cooled to
Room temperature, adds 15 grams of propylamine MTESs, reacts 180 minutes at 65 DEG C, is cooled to room temperature and can be polymerized
Thing 1.Hydroxyl is 1:2 with the mol ratio of-nco of tdi.
This polymer 1 is in light yellow transparent liquid；
This polymer 1 viscosity: 3000～12000mpa.s；
Add 2% MTMS in polymer 1, test and obtain following performance:
Surface drying time: 3～20 minutes
24 hours curing depths: > 2mm
Interiors of products bubble-free after solidification.
Embodiment 2
Essentially the same with embodiment 1, except that, choose poly(propylene oxide) ppg3000 that end is hydroxyl, in reaction
Add this polyether polyol in bottle, be subsequently adding 4,4 '-methyl diphenylene diisocyanate (mdi), hydroxyl is with-the nco's of mdi
Mol ratio is 2:1, adds catalyst organic titanium, reacts 180 minutes at 60 DEG C, is subsequently cooled to room temperature, adds ethamine first
Base trimethoxy silane, reacts 180 minutes at 65 DEG C, is cooled to room temperature and can get polymer 2.
This polymer 2 is in light yellow transparent liquid
This polymer 2 viscosity: 3000～12000mpa.s
Add 2% MTMS in polymer 2, test and obtain following performance:
Surface drying time: 3～20 minutes
24 hours curing depths: > 2mm
Interiors of products bubble-free after solidification.
Embodiment 3
Essentially the same with embodiment 1, except that, choose poly(propylene oxide) ppg6500 that end is hydroxyl, in reaction
Add this polyether polyol in bottle, be subsequently adding hexamethylene diisocyanate (hdi), the mol ratio of-nco of hydroxyl and hdi
For 1:2, add catalyst organic titanium, react 120 minutes at 130 DEG C, be subsequently cooled to room temperature, add anilinomethyl three second
TMOS, reacts 180 minutes at 65 DEG C, is cooled to room temperature and can get polymer 3.This polymer 3 is in pale yellow transparent liquid
Body；
This polymer 3 viscosity: 3000～12000mpa.s；
Add 2% MTMS in polymer 3, test and obtain following performance:
Surface drying time: 3～20 minutes
24 hours curing depths: > 2mm
Interiors of products bubble-free after solidification.
Embodiment 4
Essentially the same with embodiment 1, except that, the molecular weight of ppg is changed into 10000, prepares polymer 4.
This polymer 4 viscosity: 3000～12000mpa.s；
Add 2% MTMS in polymer 4, test and obtain following performance:
Surface drying time: 3～20 minutes
24 hours curing depths: > 2mm
Interiors of products bubble-free after solidification.
Experimental example
Polymer 1 that embodiment 1～4 is prepared, polymer 2, polymer 3, polymer 4 and buy on the market
Common silane end capped polyurethane has carried out performance test contrast: wherein colorability is scored with 1～5, and 1 point represents coloring
Ability is very weak, and 2 points represent that colorability is medium, and 3～4 points represent that colorability is medium on the upper side, and 5 points represent that colorability is very strong.
| Tensile strength (mpa) | Percentage elongation (%) | Colorability | |
| Embodiment 1 | 0.98 | 286 | 5 |
| Embodiment 2 | 0.88 | 272 | 4 |
| Embodiment 3 | 0.95 | 283 | 4 |
| Embodiment 4 | 0.92 | 287 | 5 |
| Comparative example | 0.52 | 152 | 1 |
Claims (8)
1. the synthetic method of α type silane end capped polyurethane is it is characterised in that comprise the following steps: selects the hydroxyl of suitable molecular weight
The polyether polyol of base end-blocking, adds the compound containing-nco, in the presence of catalyst, is heated to 60 ~ 130 DEG C and is reacted
60 ~ 180 minutes, it is subsequently adding α type amino silane, be heated to 60 ~ 130 DEG C and carry out reacting 60 ~ 180 minutes, finally give silane
The polyurethane of end-blocking；The structure of described α type amino silane is r1nhch2si(or)3, wherein, r1For phenyl, ethyl, propyl group；R is
Methoxyl group or ethyoxyl.
2. the synthetic method of α type silane end capped polyurethane according to claim 1 is it is characterised in that described polyether polyols
Alcohol molecular weight is 3000 ~ 10000.
3. the synthetic method of α type silane end capped polyurethane according to claim 1 is it is characterised in that described polyether polyols
In alcohol hydroxy-end capped or hydroxy-end capped while side chain also contain hydroxyl.
4. α type silane end capped polyurethane according to claim 1 synthetic method it is characterised in that described containing-nco's
Compound is one of tdi, mdi or hdi.
5. the synthetic method of α type silane end capped polyurethane according to claim 1 is it is characterised in that described polyether polyols
The hydroxyl of alcohol is 2:1 ~ 1:2 with the mol ratio of-nco of compound containing-nco.
6. the synthetic method of α type silane end capped polyurethane according to claim 1 is it is characterised in that described catalyst is
Organic titanium.
7. the α type silane end capped polyurethane of the legal manner synthesis described in claim 1 ~ 6.
8. application in terms of preparation chemical products for the α type silane end capped polyurethane described in claim 7.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610765481.4A CN106366278A (en) | 2016-08-30 | 2016-08-30 | Synthesis method of alpha type silane terminated polyurethane |
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|---|---|---|---|
| CN201610765481.4A CN106366278A (en) | 2016-08-30 | 2016-08-30 | Synthesis method of alpha type silane terminated polyurethane |
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| CN106366278A true CN106366278A (en) | 2017-02-01 |
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| CN201610765481.4A Pending CN106366278A (en) | 2016-08-30 | 2016-08-30 | Synthesis method of alpha type silane terminated polyurethane |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134887A (en) * | 2007-08-22 | 2008-03-05 | 中山大学 | Autocatalysis cross-linking organosilicon seal glue and method for making same |
| CN102482486A (en) * | 2009-08-17 | 2012-05-30 | 旭硝子株式会社 | Curable composition |
| CN103694946A (en) * | 2013-12-20 | 2014-04-02 | 湖北新蓝天新材料股份有限公司 | Method for producing silane modified polyurethane sealant by using secondary amino alpha-silane |
| CN103897649A (en) * | 2014-03-12 | 2014-07-02 | 南京艾布纳密封技术有限公司 | Method for preparing single-component silane modified polyurethane sealant |
| US20150068661A1 (en) * | 2013-09-11 | 2015-03-12 | Dow Global Technologies Llc | Silyl terminated prepolymers, method for making them and adhesive compositions made therefrom |
| CN105829377A (en) * | 2013-12-16 | 2016-08-03 | 莫门蒂夫性能材料股份有限公司 | Process for the preparation of silylated polyurethane polymers using titanium-containing and zirconium-containing catalysts |
-
2016
- 2016-08-30 CN CN201610765481.4A patent/CN106366278A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134887A (en) * | 2007-08-22 | 2008-03-05 | 中山大学 | Autocatalysis cross-linking organosilicon seal glue and method for making same |
| CN102482486A (en) * | 2009-08-17 | 2012-05-30 | 旭硝子株式会社 | Curable composition |
| US20150068661A1 (en) * | 2013-09-11 | 2015-03-12 | Dow Global Technologies Llc | Silyl terminated prepolymers, method for making them and adhesive compositions made therefrom |
| CN105829377A (en) * | 2013-12-16 | 2016-08-03 | 莫门蒂夫性能材料股份有限公司 | Process for the preparation of silylated polyurethane polymers using titanium-containing and zirconium-containing catalysts |
| CN103694946A (en) * | 2013-12-20 | 2014-04-02 | 湖北新蓝天新材料股份有限公司 | Method for producing silane modified polyurethane sealant by using secondary amino alpha-silane |
| CN103897649A (en) * | 2014-03-12 | 2014-07-02 | 南京艾布纳密封技术有限公司 | Method for preparing single-component silane modified polyurethane sealant |
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Application publication date: 20170201 |
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