CN112795001A - Low-modulus silane modified polyether and preparation method and application thereof - Google Patents
Low-modulus silane modified polyether and preparation method and application thereof Download PDFInfo
- Publication number
- CN112795001A CN112795001A CN202011603803.8A CN202011603803A CN112795001A CN 112795001 A CN112795001 A CN 112795001A CN 202011603803 A CN202011603803 A CN 202011603803A CN 112795001 A CN112795001 A CN 112795001A
- Authority
- CN
- China
- Prior art keywords
- polyether
- parts
- modified polyether
- silane
- silane modified
- 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.)
- Pending
Links
Classifications
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/322—Polymers modified by chemical after-treatment with inorganic compounds containing hydrogen
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/324—Polymers modified by chemical after-treatment with inorganic compounds containing oxygen
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention provides a low-modulus silane modified polyether, which comprises the following structural formula I and structural formula II:
whereinR is-CH3，R1And R2is-H or-CH3，R3Is C10‑C18Alkane, a is 80-500, b is 60-300, n is 2 or 3. Firstly, using monofunctional polyether and bifunctional polyether as mixed initiator, and reacting with propylene oxide under the action of bimetallic complex catalyst to obtain polyether with special structure; then, allylation reaction is carried out, and refined desalting is carried out to obtain allyl terminated polyether; and then carrying out hydrosilylation reaction with hydrogen-containing silane to prepare the low-modulus silane modified polyether. Compared with the prior art, the low-modulus silane modified polyether has higher elastic recovery rate, lower modulus, excellent sealing and bonding performance, flame retardant performance, aging resistance and storage stability, and adopts a continuous production process, so that the production efficiency is high, the material consumption and energy consumption are low, and the performance is more stable.
Description
Technical Field
The invention relates to the technical field of sealants, in particular to low-modulus silane modified polyether and a preparation method thereof, and a sealant using the silane modified polyether and a preparation method and application thereof.
Background
With the strong support and popularization of the fabricated building in China and the continuous emergence of relevant policies and standards of various places, the fabricated building in China gradually progresses and develops in a rapid development stage and gradually grows. Compared with the traditional building mode, the assembly type building mode has the advantages of energy conservation, environmental protection, high production efficiency and the like. The sealant is used as the most main caulking sealant for the fabricated building, is mainly applied to the connection and sealing among various components, particularly prefabricated external wall panels (PC wall panels), and also meets the rapid development period.
The sealant is used as a sealing and waterproof material of the fabricated building, and the quality of the sealant directly influences the quality of the fabricated building, so that the field of the fabricated building puts forward a series of requirements on the sealant: (1) adhesion and displacement capability: the concrete surface is loose and porous, the effective bonding area is reduced, and the common sealant which needs to bear larger displacement stress at the splicing part can not meet the performance requirement. In addition, concrete belongs to an alkaline material, and in areas with heavy rain and high humidity, an alkali-resistant phenomenon can occur, so that a bonding interface can be damaged, and the sealant for the fabricated building has excellent bonding performance and displacement resistance. (2) Weather resistance: the sealant for the fabricated building is directly exposed in the outdoor environment and is irradiated by sunlight and washed by rainwater for a long time, so that the sealant is required to have good weather resistance. (3) Coatability: for the prefabricated wall surface needing to be coated, the sealant also needs to have excellent paintability, and the sealant and the coating have good compatibility and can be directly coated.
The common sealant for the fabricated building mainly comprises Silicone (SR) building sealant, Polyurethane (PU) building sealant and silane modified polyether (MS) building sealant. The silicone sealant has good weather resistance and rebound resilience, but has poor adhesion performance and paintability to concrete; the polyurethane sealant has excellent bonding effect and surface paintability on concrete, but has poor weather resistance and is easy to yellow and crack; the silane modified polyether sealant has good concrete adhesion, surface paintability, weather resistance and the like, and is a mainstream product of the assembled sealant in China. However, with the continuous development of the industry, the assembly type building has higher requirements on lower modulus, higher resilience performance, flame retardance of the sealant, constructability and other comprehensive properties.
In view of the above, there is an urgent need to develop a silane modified polyether and its sealant with lower modulus, higher elastic recovery rate and excellent comprehensive properties.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide silane modified polyether with low modulus and high elastic recovery rate, a preparation method thereof, a sealant using the silane modified polyether and a preparation method thereof.
To achieve the above objects, one embodiment of the present invention provides a low modulus silane-modified polyether comprising the following structural formula I and structural formula II:
wherein R is-CH3，R1And R2is-H or-CH3，R3Is C10-C18Alkane, a is 80-500, b is 60-300, n is 2 or 3.
An embodiment of the present invention further provides a method for preparing the low-modulus silane-modified polyether, which comprises the following steps:
(1) preparing polyether with a special structure: adding a mixed initiator comprising monofunctional polyether and bifunctional polyether and a DMC catalyst into a reaction kettle, and continuously introducing propylene oxide for reaction to obtain polyether with a special structure;
(2) preparation of allyl terminated polyether: carrying out alcohol salinization reaction on the polyether with the special structure and an alcohol salinization reagent under the protection of nitrogen, then adding allyl chloride for mixed reaction, and then carrying out refined desalting to obtain allyl-terminated polyether;
(3) preparation of silane modified polyether: under the protection of nitrogen, adding a chloroplatinic acid solution into the allyl-terminated polyether, then adding hydrogen-containing silane to perform hydrosilylation reaction, and then removing unreacted silane under reduced pressure to prepare the silane-modified polyether;
wherein the mixed starter comprises the following structural formula III and structural formula IV:
the structural polyether comprises the following structural formula V and structural formula VI:
the allyl-terminated polyether includes the following structural formula VII and VIII:
wherein c is 6 to 12 and d is 10 to 18.
The invention also provides a low-modulus silane modified polyether sealant which is prepared from the following substances in parts by weight: 25-40 parts of the low-modulus silane modified polyether, 40-60 parts of a filler, 15-30 parts of a plasticizer, 2-5 parts of a thixotropic agent, 1-10 parts of a flame retardant, 1-5 parts of a water absorbent, 0.5-5 parts of a silane coupling agent, 0.5-2 parts of a light stabilizer, 0.5-2 parts of an antioxidant and 0.2-2 parts of a catalyst.
The embodiment of the invention also provides a preparation method of the low-modulus silane modified polyether sealant, which comprises the following steps: according to the metering proportion of each component, firstly, the silane modified polyether, the filler, the plasticizer, the thixotropic agent, the flame retardant, the light stabilizer and the antioxidant are subjected to vacuum treatment for 1-2 hours at 50-90 ℃, and then are dispersed at high speed for 0.5-1 hour; and then cooling to 30-40 ℃, adding a water absorbent, a silane coupling agent and a catalyst, and dispersing for 0.2-0.5 h at a high speed in vacuum to obtain the silane modified polyether sealant.
The invention further provides an application of the silane modified polyether sealant, and the silane modified polyether sealant is applied to the fields of fabricated buildings, automobiles and containers.
Compared with the prior art, the silane modified polyether and the sealant thereof have the following advantages:
the silane modified polyether is a composite product prepared from monofunctional polyether and bifunctional polyether, and the introduction of a monofunctional structure can effectively reduce the modulus and improve the elasticity. Further, the higher the molecular weight, the better the elasticity; the lower the molecular weight, the higher the strength; through the multi-aspect design of the structure of the silane modified polyether, the elastic recovery rate, the displacement resistance and the bonding performance of the product are effectively improved. In addition, the silane modified polyether does not contain carbamate, and is green and environment-friendly.
The silane modified polyether sealant disclosed by the invention adopts the synergistic effect of the flame-retardant filler and the flame retardant, has excellent flame retardant performance, can reach FV-0 level, and is suitable for bonding and sealing occasions with high requirements on flame retardant performance. Meanwhile, the sealant is matched with an antioxidant and a light stabilizer for use, so that the sealant has excellent temperature resistance and aging resistance and is wider in application range.
The invention realizes the continuous production process of the silane modified polyether and the sealant thereof, effectively reduces the influence of moisture and humidity on the product quality, and has higher production efficiency and more stable quality. In the preparation process of the sealant, the filler does not need to be subjected to heat treatment in advance, and a mixing treatment process of the filler, a plasticizer, a flame retardant, a light stabilizer, an antioxidant and the like is adopted, so that the dispersion effect is better, the storage stability and the deep curing performance of the sealant can be effectively improved, and the sealant has excellent bonding strength without a primer coating process.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
One embodiment of the present invention provides a low modulus silane-modified polyether comprising the following structural formula I and structural formula II:
in the formula, R is-CH3，R1And R2is-H or-CH3，R3Is C10-C18Alkane, a is 80 to 500, b is 60 to 300, n is 2 or3。
An embodiment of the present invention further provides a preparation method of a low modulus silane modified polyether, which includes the following steps:
(1) preparing polyether with a special structure: adding a mixed initiator comprising monofunctional polyether and bifunctional polyether and a double metal cyanide complex (DMC) catalyst into a reaction kettle, and continuously introducing propylene oxide to react to obtain polyether with a special structure;
(2) preparation of allyl terminated polyether: carrying out alcohol salinization reaction on the polyether with the special structure and an alcohol salinization reagent under the protection of nitrogen, then adding allyl chloride for mixed reaction, and carrying out refined desalting to obtain allyl-terminated polyether;
(3) preparation of silane modified polyether: under the protection of nitrogen, adding a chloroplatinic acid solution into the allyl-terminated polyether, then adding hydrogen-containing silane to perform hydrosilylation reaction, and then removing unreacted silane under reduced pressure to prepare the silane-modified polyether.
Wherein the mixed starter comprises the following structural formula III and structural formula IV:
the structural polyether comprises the following structural formula V and structural formula VI:
the allyl-terminated polyether includes the following structural formula VII and VIII:
in the formula, R1And R2is-H or-CH3，R3Is C10-C18Alkane, c is 6 to 12, d is 10 to 18, a is 80 to 500, and b is 60 to 300.
In the step (1), the reaction temperature can be 90-140 ℃, the propylene oxide is heated to the reaction temperature in the reaction kettle and then is introduced into the reaction kettle, and reacts with the mixed initiator under the action of the DMC catalyst. Optionally, the molecular weight of the mixed initiator is 400-1200 g & mol-1。
In the step (2), the polyether with the special structure obtained in the step (1) is conveyed to another reaction kettle to react with the alcohol salinization reagent, wherein the reaction temperature of the alcohol salinization reaction can be controlled to be 100-130 ℃, and the reaction time can be controlled to be 6-7 h; and during mixing reaction, the pressure in the reaction kettle is controlled to be 0.3-0.5 MPa, the reaction temperature is controlled to be 60-70 ℃, and the reaction time is controlled to be 5-7 hours. In some embodiments, the alkoxide reagent includes at least one of potassium tert-butoxide, sodium hydride, potassium methoxide, and potassium hydroxide.
Optionally, the fine desalting in step (2) comprises: and adding an acid solution for neutralization until the pH value is 4-6, and then adding a silicon-magnesium adsorbent for adsorption and filtration to obtain the allyl terminated polyether.
In some embodiments, the hydrosilane may be, but is not limited to, at least one of methyldimethoxysilane, trimethoxysilane.
The invention also provides a low-modulus silane modified polyether sealant which is prepared from the following substances in parts by weight: 25-40 parts of low-modulus silane modified polyether, 40-60 parts of filler, 15-30 parts of plasticizer, 2-5 parts of thixotropic agent, 1-10 parts of flame retardant, 1-5 parts of water absorbent, 0.5-5 parts of silane coupling agent, 0.5-2 parts of light stabilizer, 0.5-2 parts of antioxidant and 0.2-2 parts of catalyst. The silane modified sealant is applied to the fields of fabricated buildings, automobiles and containers.
In some embodiments, the filler comprises at least two of nano calcium carbonate, ground calcium carbonate, titanium dioxide, aluminum hydroxide, magnesium hydroxide.
In some embodiments, the plasticizer comprises at least one of dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, polypropylene glycol.
In some embodiments, the thixotropic agent comprises at least one of a polyamide wax, an organobentonite, a hydroxy silicone oil.
In some embodiments, the flame retardant comprises at least two of triphenyl phosphate, tricresyl phosphate, tributyl phosphonate, antimony pentoxide, zinc borate, zinc oxide.
In some embodiments, the water absorbing agent comprises at least one of KH171, KH151, KH-3112, HMDSO.
In some embodiments, the light stabilizer comprises at least one of 326, 329, 770, 765.
In some embodiments, the antioxidant comprises at least one of 1010, 1035, 1076, 245, 168.
In some embodiments, the silane coupling agent comprises at least one of KH540, KH550, KH560, KH 792, 1146.
In some embodiments, the catalyst comprises at least one of dibutyltin dilaurate, zinc isooctanoate, bismuth octyldecanoate.
The embodiment of the invention also provides a preparation method of the low-modulus silane modified polyether sealant, which comprises the following steps: according to the metering proportion of each component, firstly, carrying out vacuum treatment on the silane modified polyether, the filler, the plasticizer, the thixotropic agent, the flame retardant, the light stabilizer and the antioxidant for 1-2 h at 50-90 ℃, and then dispersing at high speed for 0.5-1 h; and then cooling to 30-40 ℃, adding a water absorbent, a silane coupling agent and a catalyst, dispersing for 0.2-0.5 h at a high speed in vacuum, filling, sealing and storing to obtain the silane modified polyether sealant.
The preparation and performance of the low modulus silane modified polyether and its sealant of the present invention are specifically illustrated by the following examples.
Example 1
(1) Preparing polyether with a special structure: the reactor was charged with a solution containing 22g of monofunctionalDegree C10Adding a mixed initiator of alkane polyether and 10g of bifunctional polyether (hydroxyl value is about 178mgKOH/g) and 0.12g of DMC catalyst, and introducing 968g of propylene oxide at 90-140 ℃ for reaction to obtain polyether (hydroxyl value is about 5mgKOH/g) with a special structure;
(2) preparation of allyl terminated polyether: carrying out alcohol salinization reaction on the obtained polyether with the special structure and 4.6g of sodium hydride with the mass fraction of 60% at 100-130 ℃ for 6-7 h under the protection of nitrogen; then adding 8.75g of allyl chloride, mixing and reacting for 5-7 h at 0.3-0.5 MPa and 60-70 ℃, neutralizing to a pH value of 4.0-6.0 by phosphoric acid, and then adding 60g of silicon-magnesium adsorbent for adsorption and filtration to obtain the allyl-terminated polyether;
(3) preparation of silane modified polyether: under the protection of nitrogen, adding 0.035g of chloroplatinic acid solution into the obtained allyl-terminated polyether, then adding 11.8g of methyldimethoxysilane, reacting for 1-5 h at 50-90 ℃, and then removing unreacted silane under reduced pressure to obtain the silane-modified polyether;
(4) preparing a silane modified sealant: preparing materials according to the following component proportion, wherein the weight parts of the components are as follows: 25 parts of silane modified polyether, 50 parts of heavy calcium carbonate, 2 parts of titanium dioxide, 3 parts of aluminum hydroxide, 25 parts of diisononyl phthalate, 2 parts of hydroxyl silicone oil, 5 parts of triphenyl phosphate, 5 parts of tricresyl phosphate, 2 parts of KH171, 0.5 part of KH 792, 0.3 part of KH560, 0.3 part of 326, 0.2 part of 765, 0.8 part of 1010 and 0.2 part of dibutyltin dilaurate; carrying out vacuum treatment on silane modified polyether, filler, plasticizer, thixotropic agent, flame retardant, light stabilizer and antioxidant at 50-90 ℃ for 1-2 h, and then dispersing at high speed for 0.5-1 h; and cooling to 30-40 ℃, adding a water absorbent, a silane coupling agent and a catalyst, dispersing for 0.2-0.5 h at a high speed in vacuum, filling, sealing and storing to obtain the silane modified polyether sealant.
Example 2
(1) Preparing polyether with a special structure: the reactor was charged with a solution containing 28.6g of monofunctional C14Adding 951g of propylene oxide into a mixed initiator (hydroxyl value is about 134mgKOH/g) of alkane polyether and 20g of bifunctional polyether and 0.10g of DMC catalyst at 90-140 ℃ to react to obtain polyether (hydroxyl value is about 5.3 m)gKOH/g)；
(2) Preparation of allyl terminated polyether: carrying out alcohol salinization reaction on the obtained polyether with the special structure, 2.6g of sodium hydride with the mass fraction of 60% and 1.4g of powdery potassium hydroxide at 100-130 ℃ for 6-7 h under the protection of nitrogen; then adding 9.3g of allyl chloride, mixing and reacting for 5-7 h at 0.3-0.5 MPa and 60-70 ℃, neutralizing to a pH value of 4.0-6.0 by phosphoric acid, and then adding 55g of silicon-magnesium adsorbent for adsorption and filtration to obtain the allyl-terminated polyether;
(3) preparation of silane modified polyether: under the protection of nitrogen, adding 0.04g of chloroplatinic acid solution into the obtained allyl-terminated polyether, then adding 12.37g of methyldimethoxysilane, reacting at 50-90 ℃ for 1-5 h, and then removing unreacted silane under reduced pressure to obtain the silane-modified polyether;
(4) preparing a silane modified sealant: preparing materials according to the following component proportion, wherein the weight parts of the components are as follows: 25 parts of silane modified polyether, 40 parts of heavy calcium carbonate, 2 parts of light calcium carbonate, 3 parts of magnesium hydroxide, 25 parts of polypropylene glycol 2000, 2 parts of polyamide wax, 3 parts of hydroxyl silicone oil, 7 parts of tributyl phosphonate, 3 parts of antimony pentoxide, 2 parts of KH151, 0.5 part of KH-3112, 0.5 part of KH 792, 0.2 part of 1146, 0.3 part of 329, 0.3 part of 765, 0.5 part of 1076, 0.5 part of 168, 0.15 part of dibutyltin dilaurate and 0.5 part of zinc isooctanoate; carrying out vacuum treatment on silane modified polyether, filler, plasticizer, thixotropic agent, flame retardant, light stabilizer and antioxidant at 50-90 ℃ for 1-2 h, and then dispersing at high speed for 0.5-1 h; and cooling to 30-40 ℃, adding a water absorbent, a silane coupling agent and a catalyst, dispersing for 0.2-0.5 h at a high speed in vacuum, filling, sealing and storing to obtain the silane modified polyether sealant.
Example 3
(1) Preparing polyether with a special structure: to the reactor was added a solution containing 34.3g of monofunctional C16A mixed initiator of alkane polyether and 10g of bifunctional polyether (hydroxyl value is about 130mgKOH/g) and 0.08g of DMC catalyst, 956g of propylene oxide is introduced at 90-140 ℃ for reaction to obtain polyether with a special structure (hydroxyl value is about 4.6 mgKOH/g);
(2) preparation of allyl terminated polyether: carrying out alcohol salinization reaction on the obtained polyether with the special structure, 2.78g of sodium hydride with the mass fraction of 60% and 2.1g of potassium methoxide for 6-7 h at the temperature of 100-130 ℃ under the protection of nitrogen; then adding 7.87g of allyl chloride, mixing and reacting for 5-7 h at 0.3-0.5 MPa and 60-70 ℃, neutralizing to a pH value of 4.0-6.0 by phosphoric acid, and then adding 60g of silicon-magnesium adsorbent for adsorption and filtration to obtain the allyl-terminated polyether;
(3) preparation of silane modified polyether: under the protection of nitrogen, adding 0.032g of chloroplatinic acid solution into the obtained allyl-terminated polyether, then adding 5.3g of methyldimethoxysilane and 6.2g of trimethoxy silane, reacting at 50-90 ℃ for 1-5 h, and then removing unreacted silane under reduced pressure to obtain the silane-modified polyether;
(4) preparing a silane modified sealant: preparing materials according to the following component proportion, wherein the weight parts of the components are as follows: 20 parts of silane-modified polyether, 40 parts of heavy calcium carbonate, 5 parts of light calcium carbonate, 5 parts of aluminum hydroxide, 20 parts of polypropylene glycol 3000, 5 parts of dioctyl phthalate, 2 parts of polyamide wax, 2 parts of organic bentonite, 8 parts of triphenyl phosphate, 2 parts of zinc borate, 1 part of KH171, 1 part of HMDSO, 0.5 part of KH 792, 0.3 part of KH540, 0.3 part of KH550, 0.5 part of 326, 0.2 part of 770, 0.2 part of 1035, 0.2 part of 245 and 0.2 part of dibutyltin dilaurate; carrying out vacuum treatment on silane modified polyether, filler, plasticizer, thixotropic agent, flame retardant, light stabilizer and antioxidant at 50-90 ℃ for 1-2 h, and then dispersing at high speed for 0.5-1 h; and cooling to 30-40 ℃, adding a water absorbent, a silane coupling agent and a catalyst, dispersing for 0.2-0.5 h at a high speed in vacuum, filling, sealing and storing to obtain the silane modified polyether sealant.
Example 4
(1) Preparing polyether with a special structure: to the reactor was added a solution containing 47.6g of monofunctional C16～18A mixed initiator of alkane polyether and 11.6g of bifunctional polyether (hydroxyl value is about 98mgKOH/g) and 0.06g of DMC catalyst, 940g of propylene oxide is introduced at 90-140 ℃ for reaction to obtain polyether with a special structure (hydroxyl value is about 4.6 mgKOH/g);
(2) preparation of allyl terminated polyether: carrying out alcohol salinization reaction on the obtained polyether with the special structure, 3.45g of sodium hydride with the mass fraction of 60% and 1.1g of powdery potassium hydroxide at 100-130 ℃ for 6-7 h under the protection of nitrogen; then adding 8.75g of allyl chloride, mixing and reacting for 5-7 h at 0.3-0.5 MPa and 60-70 ℃, neutralizing to a pH value of 4.0-6.0 by phosphoric acid, and then adding 70g of silicon-magnesium adsorbent for adsorption and filtration to obtain the allyl-terminated polyether;
(3) preparation of silane modified polyether: under the protection of nitrogen, adding 0.028g of chloroplatinic acid solution into the obtained allyl-terminated polyether, then adding 7.5g of methyldimethoxysilane and 2.8g of trimethoxy silane, reacting at 50-90 ℃ for 1-5 h, and then removing unreacted silane under reduced pressure to obtain the silane-modified polyether;
(4) preparing a silane modified sealant: preparing materials according to the following component proportion, wherein the weight parts of the components are as follows: 30 parts of silane modified polyether, 40 parts of heavy calcium carbonate, 2 parts of titanium dioxide, 3 parts of magnesium hydroxide, 15 parts of polypropylene glycol 4000, 10 parts of diisodecyl phthalate, 2 parts of polyamide wax, 6 parts of tricresyl phosphate, 4 parts of zinc borate, 1.2 parts of KH171, 0.6 part of KH-3112, 0.5 part of KH 792, 0.5 part of 1146, 0.3 part of 329, 0.2 part of 770, 0.2 part of 1010, 0.4 part of 1035, 0.15 part of dibutyltin dilaurate and 0.1 part of bismuth octyldecanoate; carrying out vacuum treatment on silane modified polyether, filler, plasticizer, thixotropic agent, flame retardant, light stabilizer and antioxidant at 50-90 ℃ for 1-2 h, and then dispersing at high speed for 0.5-1 h; and cooling to 30-40 ℃, adding a water absorbent, a silane coupling agent and a catalyst, dispersing for 0.2-0.5 h at a high speed in vacuum, filling, sealing and storing to obtain the silane modified polyether sealant.
The silane-modified polyethers and silane-modified polyether sealants prepared in examples 1 to 4 were subjected to performance tests, the test standards and test results of which are shown in table 1.
TABLE 1
It can be seen from table 1 that the modified polyether and the sealant thereof of each example have low viscosity, easy operation, good workability, low modulus, high elastic recovery rate, excellent sealing and bonding properties and flame retardant properties, and are suitable for fields such as assembly buildings, automobiles and containers with high requirements on flame retardant properties.
In addition, other modifications within the spirit of the invention will occur to those skilled in the art, and it is understood that such modifications are included within the scope of the invention as claimed.
Claims (10)
1. A low modulus silane modified polyether comprising the following structural formula I and structural formula II:
wherein R is-CH3，R1And R2is-H or-CH3，R3Is C10-C18Alkane, a is 80-500, b is 60-300, n is 2 or 3.
2. The process for preparing the low modulus silane modified polyether of claim 1 comprising the steps of:
(1) preparing polyether with a special structure: adding a mixed initiator comprising monofunctional polyether and bifunctional polyether and a DMC catalyst into a reaction kettle, and continuously introducing propylene oxide for reaction to obtain polyether with a special structure;
(2) preparation of allyl terminated polyether: carrying out alcohol salinization reaction on the polyether with the special structure and an alcohol salinization reagent under the protection of nitrogen, then adding allyl chloride for mixed reaction, and then carrying out refined desalting to obtain allyl-terminated polyether;
(3) preparation of silane modified polyether: under the protection of nitrogen, adding a chloroplatinic acid solution into the allyl-terminated polyether, then adding hydrogen-containing silane to perform hydrosilylation reaction, and then removing unreacted silane under reduced pressure to prepare the silane-modified polyether;
wherein the mixed starter comprises the following structural formula III and structural formula IV:
the structural polyether comprises the following structural formula V and structural formula VI:
the allyl-terminated polyether includes the following structural formula VII and VIII:
wherein c is 6 to 12 and d is 10 to 18.
3. The method of claim 2 wherein the alcoholation agent is at least one of potassium tert-butoxide, sodium hydride, potassium methoxide and potassium hydroxide.
4. The method of claim 2, wherein the hydrosilane is at least one of methyldimethoxysilane and trimethoxysilane.
5. A low-modulus silane modified polyether sealant is composed of the following substances in parts by weight: 25 to 40 parts of the silane-modified polyether according to claim 1, 40 to 60 parts of a filler, 15 to 30 parts of a plasticizer, 2 to 5 parts of a thixotropic agent, 1 to 10 parts of a flame retardant, 1 to 5 parts of a water absorbent, 0.5 to 5 parts of a silane coupling agent, 0.5 to 2 parts of a light stabilizer, 0.5 to 2 parts of an antioxidant, and 0.2 to 2 parts of a catalyst.
6. The low modulus silane modified polyether sealant of claim 5 wherein the filler is at least two of nano calcium carbonate, ground calcium carbonate, titanium dioxide, aluminum hydroxide, magnesium hydroxide.
7. The low modulus silane modified polyether sealant of claim 5 wherein the flame retardant is at least two of triphenyl phosphate, tricresyl phosphate, tributyl phosphonate, antimony pentoxide, zinc borate, zinc oxide.
8. The low modulus silane modified polyether sealant of claim 5 wherein the plasticizer is at least one of dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, polypropylene glycol; the thixotropic agent is at least one of polyamide wax, organic bentonite and hydroxyl silicone oil; the catalyst is at least one of dibutyltin dilaurate, zinc isooctanoate and bismuth octyldecanoate; the water absorbent is at least one of KH171, KH151, KH-3112 and HMDSO; the light stabilizer is at least one of 326, 329, 770 and 765; the antioxidant is at least one of 1010, 1035, 1076, 245 and 168; the silane coupling agent is at least one of KH540, KH550, KH560, KH 792 and 1146.
9. The process for preparing a low modulus silane modified polyether sealant as claimed in any one of claims 5 to 8, which comprises the steps of: according to the metering proportion of each component, firstly, the silane modified polyether, the filler, the plasticizer, the thixotropic agent, the flame retardant, the light stabilizer and the antioxidant are subjected to vacuum treatment for 1-2 hours at 50-90 ℃, and then are dispersed at high speed for 0.5-1 hour; and then cooling to 30-40 ℃, adding a water absorbent, a silane coupling agent and a catalyst, and dispersing for 0.2-0.5 h at a high speed in vacuum to obtain the silane modified polyether sealant.
10. Use of the low modulus silane modified polyether sealant according to any one of claims 5 to 8 in the fields of fabricated construction, automotive and container applications.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011603803.8A CN112795001A (en) | 2020-12-30 | 2020-12-30 | Low-modulus silane modified polyether and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011603803.8A CN112795001A (en) | 2020-12-30 | 2020-12-30 | Low-modulus silane modified polyether and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112795001A true CN112795001A (en) | 2021-05-14 |
Family
ID=75804306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011603803.8A Pending CN112795001A (en) | 2020-12-30 | 2020-12-30 | Low-modulus silane modified polyether and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112795001A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929897A (en) * | 2021-11-01 | 2022-01-14 | 江西晨光新材料股份有限公司 | Silane modified esterified polyether and preparation method and application thereof |
| CN113956487A (en) * | 2021-11-23 | 2022-01-21 | 湖南松井新材料股份有限公司 | Silane modified polyether and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0496109A2 (en) * | 1990-12-26 | 1992-07-29 | UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY CORPORATION, Three Cristina Centre | A process for producing alkoxysilane-terminated polyethers |
| US20120029090A1 (en) * | 2010-08-02 | 2012-02-02 | Evonik Goldschmidt Gmbh | Modified alkoxylation products having at least one non-terminal alkoxysilyl group, with increased storage life and increased stretchability of the polymers prepared using them |
| CN104448284A (en) * | 2014-11-28 | 2015-03-25 | 浙江皇马科技股份有限公司 | Preparation method of diallyl-capped polyether |
| CN105176469A (en) * | 2015-08-07 | 2015-12-23 | 常州艾卡新材料科技有限公司 | Preparation method of silane modified polyether sealant for building |
| CN107892900A (en) * | 2017-12-01 | 2018-04-10 | 北京东方雨虹防水技术股份有限公司 | Single component silane modified polyether seal glue of the low high resilience of modulus and preparation method thereof |
| CN109293911A (en) * | 2018-09-30 | 2019-02-01 | 烟台德邦科技有限公司 | A kind of preparation method of end silicone based polyether resin |
| CN110041871A (en) * | 2019-04-11 | 2019-07-23 | 上海东大化学有限公司 | A kind of silane modified polyether seal glue and preparation method thereof |
| CN111073575A (en) * | 2019-12-31 | 2020-04-28 | 江苏瑞洋安泰新材料科技有限公司 | Single-component silane modified polyether sealant for prefabricated building and preparation method thereof |
| WO2020133062A1 (en) * | 2018-12-27 | 2020-07-02 | 万华化学集团股份有限公司 | Method for preparing reactive sealant resin |
| CN112029465A (en) * | 2020-09-17 | 2020-12-04 | 郑州大学 | Low-modulus MS sealant for assembly type building outer wall and preparation method thereof |
-
2020
- 2020-12-30 CN CN202011603803.8A patent/CN112795001A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0496109A2 (en) * | 1990-12-26 | 1992-07-29 | UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY CORPORATION, Three Cristina Centre | A process for producing alkoxysilane-terminated polyethers |
| US20120029090A1 (en) * | 2010-08-02 | 2012-02-02 | Evonik Goldschmidt Gmbh | Modified alkoxylation products having at least one non-terminal alkoxysilyl group, with increased storage life and increased stretchability of the polymers prepared using them |
| CN104448284A (en) * | 2014-11-28 | 2015-03-25 | 浙江皇马科技股份有限公司 | Preparation method of diallyl-capped polyether |
| CN105176469A (en) * | 2015-08-07 | 2015-12-23 | 常州艾卡新材料科技有限公司 | Preparation method of silane modified polyether sealant for building |
| CN107892900A (en) * | 2017-12-01 | 2018-04-10 | 北京东方雨虹防水技术股份有限公司 | Single component silane modified polyether seal glue of the low high resilience of modulus and preparation method thereof |
| CN109293911A (en) * | 2018-09-30 | 2019-02-01 | 烟台德邦科技有限公司 | A kind of preparation method of end silicone based polyether resin |
| WO2020133062A1 (en) * | 2018-12-27 | 2020-07-02 | 万华化学集团股份有限公司 | Method for preparing reactive sealant resin |
| CN110041871A (en) * | 2019-04-11 | 2019-07-23 | 上海东大化学有限公司 | A kind of silane modified polyether seal glue and preparation method thereof |
| CN111073575A (en) * | 2019-12-31 | 2020-04-28 | 江苏瑞洋安泰新材料科技有限公司 | Single-component silane modified polyether sealant for prefabricated building and preparation method thereof |
| CN112029465A (en) * | 2020-09-17 | 2020-12-04 | 郑州大学 | Low-modulus MS sealant for assembly type building outer wall and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929897A (en) * | 2021-11-01 | 2022-01-14 | 江西晨光新材料股份有限公司 | Silane modified esterified polyether and preparation method and application thereof |
| CN113956487A (en) * | 2021-11-23 | 2022-01-21 | 湖南松井新材料股份有限公司 | Silane modified polyether and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111394034B (en) | Single-component silane modified polyether sealant for prefabricated building and preparation method thereof | |
| CN109880569B (en) | Epoxy resin modified MS sealant | |
| CN112795001A (en) | Low-modulus silane modified polyether and preparation method and application thereof | |
| CN103087666B (en) | Reactive type polyurethane hot-melt sealant | |
| CN103910847A (en) | Silane terminated polyurethane oligomer and its preparation method | |
| CN102746486B (en) | Single-component bonding sealing type silicone adhesive for solar battery assembly | |
| CN103320079A (en) | Preparation method of flame retardant single-component silane modified polyether sealant | |
| CN104263315B (en) | A kind of acid transparent silicone weather proofing sealant for building | |
| CN110105907B (en) | Single-component silane modified polyether sealant for quick assembly of automobile glass and preparation method thereof | |
| CN108179003B (en) | Dealcoholized silicone weather-resistant sealant with low modulus and high displacement capacity and preparation method thereof | |
| CN109280528A (en) | A kind of High-strength double-component polyurethane group angle glue and preparation method thereof | |
| CN113337245B (en) | Dealcoholized photovoltaic module sealant and preparation method thereof | |
| CN111073575A (en) | Single-component silane modified polyether sealant for prefabricated building and preparation method thereof | |
| CN113185947B (en) | Mixed crosslinking system two-component hollow sealant | |
| CN103059800B (en) | Silane-terminiated polysulfide rubber sealant and preparation method thereof | |
| WO2019127239A1 (en) | Low-modulus high-adhesion fabricated silane modified polyether adhesive used for building, and preparation method therefor | |
| CN114805788B (en) | Aminosilane modified tackifier, high-water-resistance silane modified polyether adhesive and preparation method thereof | |
| CN113684003B (en) | Two-component room temperature vulcanized silicone rubber composition | |
| CN111073577B (en) | Environment-friendly MS sealant and preparation method thereof | |
| CN113528080B (en) | High-displacement anti-pollution silicone sealant and preparation method thereof | |
| CN105199661B (en) | A kind of silicone sealant of high elongation rate and preparation method thereof | |
| CN104893642A (en) | High-strength flame retardant polyurethane sealant | |
| CN112694864B (en) | Silicone sealant, preparation method thereof and photovoltaic module | |
| CN110128996A (en) | Sealant and its preparation method and application and vehicle | |
| CN114702935B (en) | Modified silane sealant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |