CN111393611B - Silane end-capped resin for sealant and preparation method thereof - Google Patents
Silane end-capped resin for sealant and preparation method thereof Download PDFInfo
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- CN111393611B CN111393611B CN202010354239.4A CN202010354239A CN111393611B CN 111393611 B CN111393611 B CN 111393611B CN 202010354239 A CN202010354239 A CN 202010354239A CN 111393611 B CN111393611 B CN 111393611B
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7678—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
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- 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
- C08G65/2639—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 elements other than oxygen, nitrogen or sulfur
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
Abstract
The invention provides silane end-capped resin for a sealant, which has the structural formula:
wherein R is a linear or branched C1-C10 alkyl group; r0Is a linear or branched C1-C10 alkyl group or a branched C1-C10 alkoxy group; r1Is a linear or branched C1-C10 alkyl group; r2Is a diisocyanate group; the invention also discloses a preparation method of the resin, which comprises the steps of taking hydroxyl alkoxy silane as a raw material, adding a first catalyst, heating after nitrogen is placed, introducing an epoxy compound for pre-reaction, continuously introducing the epoxy compound for reaction after the initiation reaction, and obtaining a monosiloxyl terminated polyether intermediate; adding a second catalyst and diisocyanate into the intermediate, and keeping the temperature to continue the reaction to obtain silane-terminated resin for the sealant; the invention shortens the reaction path, thereby reducing side reaction, improving the utilization rate of raw materials, generating no three wastes in the preparation process, having simple and environment-friendly preparation process and lower dynamic viscosity of the prepared resin.
Description
Technical Field
The invention relates to the technical field of polymers, in particular to silane end-capped resin for a sealant and a preparation method thereof.
Background
The silane terminated resin has the flexibility and low temperature resistance of polyether, and the silane terminated group has good moisture curing property and cohesiveness, and is a main raw material of an adhesive and a sealant. In recent years, the silane-terminated polyether has been rapidly researched and applied to the fields of super high-rise buildings, rail transit and traceless assembly due to excellent adhesive property and processability.
The emphasis in the study of silane-terminated resins was on the silane modification technology, and at the earliest in the 70-80 th 20 th century, the Japanese Kaneka company first proposed a method for preparing a silane-terminated resin by using polypropylene oxide as a main chain and using dimethoxysilane for termination; and Kaneka company named "Cauchi MS Polymer" in 1979 for an industrialized silane-terminated resin-based sealant; the synthesis is usually completed by a 2-step method: step 1: taking allyl polyether alcohol, hydroxyl-terminated polyether and the like as raw materials, taking methylene dihalide as a chain extender and caustic alkali as a catalyst, and carrying out chain extension reaction to prepare an allyl-terminated polyether intermediate; step 2: in the presence of a platinum catalyst, the refined polyether intermediate reacts with methyldimethoxysilane through end-silylation reaction to prepare silane modified polyether, and the synthetic route is as follows:
the first step is as follows:
the second step is that:
the same technical method for modifying polyether by using hydrosilation method is disclosed in patent CN 108102089A, which is different from the second step of the clocked MS polymer, and the synthetic route is as follows:
the diallyl polyether intermediate is used in the processes, and allyl alcohol polyether with proper molecular weight is obtained by chain extension of low molecular weight allyl polyoxypropylene ether and polypropylene glycol (PPG) and finally is prepared by allyl end capping.
The method needs to react with PPG for many times, removes salt and refines for many times, increases the generated solid waste, reduces the yield, has more complicated process steps, obtains more byproducts, and finally obtains the product with too wide molecular weight distribution because the reaction polymerization in each step is incomplete, and the product performance of the prepared MS sealant is limited.
At the same time, U.S. general purpose company blocked polyethers with hydrolyzable isocyanatoalkoxysilane containing, moisture curable polymers were prepared, opening the door to silane blocked polyurethane resins. The main methods for preparing silane-terminated polyurethane resins reported in the literature can be broadly divided into two types, one is that hydroxyl-terminated polyether is directly reacted with alkoxy silane with NCO functional group to prepare silane-terminated polyurethane resin, and the reaction is as follows:
although the process is simple, the alkoxysilane containing NCO groups is expensive, the finished product of the product is high, the product has small profit space, and the market competitiveness is poor.
In order to avoid the use of expensive alkoxysilanes containing NCO groups, the patent CN 105199653B describes a two-component resin PU-SPU. The patent adopts hydroxyl-terminated polyether to react with diisocyanate to obtain NCO-terminated prepolymer PU, and then the prepolymer PU reacts with aminosilane to prepare silane-terminated polyurethane resin SPU, wherein the reaction formula is as follows:
PU：
SPU：
the process has the advantages that the conventional raw materials are adopted, the market popularization is easy, the process is also the mainstream method for producing the silane-terminated polyurethane resin in the current market, but three steps of reactions (the preparation process mentioned above, the step of obtaining the dihydroxy polyether from the epoxy compound, and the step are actually three steps of reactions) are needed to obtain the product, and each step of reaction has the possibility of generating side reactions, so that the raw materials are consumed; and the molecular chain contains strong polar urethane bonds, so that hydrogen bonds are formed between polymer molecules and in the polymer molecules, the dynamic viscosity of the system is increased, and finally the poor extrusion property of the glue in the application process is caused.
In combination with the current situation of the silane-terminated resin, it is important to develop a novel silane-terminated resin with low dynamic viscosity, which is prepared from general raw materials by a simple preparation process.
Disclosure of Invention
Aiming at the technical problems, in order to solve the problems of complex preparation technology, expensive raw materials and high product dynamic viscosity of the existing silane terminated resin, the invention provides the silane terminated resin for the sealant and a preparation method thereof, wherein the silane terminated resin with low dynamic viscosity is obtained by selecting the conventional raw materials through a simple and environment-friendly preparation process, and the specific scheme is as follows:
a silane end-capped resin for sealant has a structural formula as follows:
wherein R is linear C1-C10 alkyl or branched C1-C10 alkyl;
R0is a linear C1-C10 alkyl group, a branched C1-C10 alkyl group or a branched C1-C10 alkoxy group;
R1is a linear C1-C10 alkyl group or a branched C1-C10 alkyl group;
R2is a diisocyanate group.
Further, said R2Having the formula NCO-R3-NCO, said R3Is composed of
Or C6H12One of them.
Further, the number average molecular weight of the silane-terminated resin for the sealant is 4000-20000.
The preparation method of the silane-terminated resin for the sealant comprises the following steps:
s1: adding a first catalyst into hydroxyl alkoxy silane serving as a raw material, placing nitrogen, heating, introducing an epoxy compound for pre-reaction, and continuously introducing the epoxy compound for reaction after initiating reaction to obtain a monosiloxyl terminated polyether intermediate;
s2: and adding a second catalyst and diisocyanate into the monosiloxane terminated polyether intermediate formed in the step S1, and keeping the temperature for continuous reaction to obtain the silane terminated resin for the sealant.
Further, step S1 is specifically: adding hydroxyl alkoxy silane into a closed reaction kettle, adding a first catalyst, completely replacing air in the reaction kettle with nitrogen, heating to 120-plus-150 ℃, adding a part of epoxy compound for an excitation reaction, after the initiation reaction, continuously introducing the rest of epoxy compound at 120-plus-150 ℃, preserving the heat at 140-plus-150 ℃ for 1 hour, and finally removing the unreacted epoxy compound to obtain a monosilicoalkyl polyether intermediate with the number average molecular weight of 2000-plus-10000; step S2 specifically includes: and after the step S1 is finished, cooling, adding a second catalyst, adding diisocyanate, and after the addition is finished, carrying out heat preservation reaction for 1-2 hours to obtain the silane-terminated resin for the sealant. Wherein the reaction temperature in step S2 is 50-100 deg.C, preferably 80-90 deg.C. Wherein the reaction time in the step (2) is 1-2 hours.
The preparation method provided by the invention has the following reaction principle:
(wherein, R is a linear C1-C10 alkyl group or a branched C1-C10 alkyl group, R0Is linear C1-C10 alkyl or branched C1-C10 alkyl or linear C1-C10 alkyl or branched C1-C10 alkoxy, R1Is a linear C1-C10 alkyl group or a branched C1-C10 alkyl group, R4Is CH3Or H);
(wherein R is a linear C1-C10 alkyl group or a branched C1-C10 alkyl group; R0Is linear C1-C10 alkyl or branched C1-C10 alkyl or linear C1-C10 alkyl or branched C1-C10 alkoxy; r1Is a linear C1-C10 alkyl group or a branched C1-C10 alkyl group; r2Comprising diisocyanate groups of the formula NCO-R3-NCO，R3Is composed of
Or C6H12One of the above).
Further, the molar ratio of the epoxy compound to the hydroxyalkoxysilane is from 35 to 280: 1.
further, the molar ratio of diisocyanate to monosiloxanyl polyether intermediate in S2 is 0.4-0.6: 1.
further, the hydroxy alkoxy silane is hydroxymethyl triethoxysilane or hydroxymethyl trimethoxysilane.
Further, the first catalyst is an alkoxylation catalyst, preferably a double metal cyanide catalyst.
Further, the epoxy compound is ethylene oxide and/or propylene oxide.
Further, the mass of the second catalyst is 200-500ppm of the total amount charged in the S1 (i.e. the total mass of the hydroxyalkoxysilane, the first catalyst, the epoxy compound used for initiating the reaction and the epoxy compound continuously fed to the reaction after the initiation reaction).
Further, the second catalyst is a stannous octoate-triethylene diamine composite catalyst, and the mass ratio of the components is 1: 0.4-0.8.
Further, the diisocyanate is one or a mixture of more than two of Toluene Diisocyanate (TDI), 1, 5-Naphthalene Diisocyanate (NDI), isophorone diisocyanate (IPDI), hydrogenated phenyl methane diisocyanate (H-MDI) and 1, 6-Hexamethylene Diisocyanate (HDI).
Compared with the prior art, the invention has the following beneficial effects:
the invention provides silane terminated resin for a sealant, which is prepared by taking hydroxyl alkoxy silane as an initiator, obtaining a monosiloxane terminated polyether intermediate through alkoxylation, and reacting hydroxyl of the intermediate with diisocyanate to obtain disiloxane terminated polymer resin, namely silane terminated resin for the sealant. Compared with the method that the main chain of the diallyl terminated polyether or the dihydroxy polyether is firstly obtained and the disilane terminated resin is obtained by hydrosilylation or polyurethane addition in the prior art, the method has the following three prominent advantages:
the conventional raw materials are selected, so that diallyl polyether with a complex preparation process or expensive alkoxy silane containing NCO groups is avoided, a raw material supply chain is shortened, and the cost can be reduced;
the reaction from epoxy compound raw materials to resin is shortened from three steps to two steps, the shortening of the reaction path can reduce side reactions, improve the utilization rate of the raw materials and reduce the energy consumption generated in the reaction process, and three wastes are not generated in the preparation process;
and the dynamic viscosity of the silane-terminated resin is relatively low, only 2 urethane bonds are introduced into each resin molecule, and the dynamic viscosity is obviously reduced compared with that of a silane-terminated polymer resin (containing 4 urethane bonds) of a polysilane polyurethane type (SPU).
In conclusion, the invention selects the conventional raw materials, the preparation process is simple and environment-friendly, the dynamic viscosity of the prepared resin is lower, and the problem of poor rubber extrudability in the application process caused by the increase of the dynamic viscosity in the prior art is solved.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following examples and comparative examples part of the equipment used for the performance tests:
1. the characteristic peak of NCO measured by infrared spectroscopy (NRUKER: TENSOR27) indicates the end point of the reaction;
2. the dynamic viscosity of the 20 silane terminated resin finished product at 25 ℃ is measured by a rheometer (TA: DHR-2).
Example 1
A silane end-capped resin for a sealant is prepared by the following steps:
s1: sequentially adding 1 part of hydroxymethyl triethoxysilane and 80ppm Double Metal Cyanide (DMC) catalyst into a 2.5L high-pressure glass reaction kettle, completely replacing air in the high-pressure glass reaction kettle with nitrogen, heating to 150 ℃ while stirring, adding 0.5 part of epoxypropane to initiate reaction, starting to continuously add the rest 34.5 parts of epoxypropane when the temperature rise speed in the reaction kettle exceeds 0.1 ℃/s and the pressure begins to drop, keeping the temperature at 150 ℃ after the addition is finished and curing for 2 hours, keeping the pressure unchanged, vacuumizing and degassing for 20 minutes to obtain a monosilicon alkyl polyether intermediate;
s2: reducing the temperature in a high-pressure glass reaction kettle to 80 ℃, transferring all monosiloxyl polyether intermediates prepared in the step S1 into a normal-pressure reaction kettle, adding 200ppm of a stannous octoate-triethylene diamine composite catalyst (the mass ratio of the stannous octoate to the triethylene diamine is 1:0.4), stirring and heating, after 10 minutes, raising the temperature to 80 ℃, then dropwise adding 0.5 part of diisocyanate, carrying out heat preservation reaction for 1 hour to obtain triethoxysilane end-capped resin with the molecular weight of about 4000, discharging and filling; sampling and measuring the infrared of the finished product, and no NCO characteristic peak.
Under the above process conditions, different diisocyanates were selected, and the dynamic viscosity of the obtained triethoxysilane-terminated resin is shown in table 1:
TABLE 1 dynamic viscosity test results for silane-terminated resins for sealants prepared from different diisocyanates
Example 2
A silane end-capped resin for a sealant is prepared by the following steps:
s1: sequentially adding 1 part of hydroxymethyl triethoxysilane and 80ppm Double Metal Cyanide (DMC) catalyst into a 2.5L high-pressure glass reaction kettle, completely replacing air in the high-pressure glass reaction kettle with nitrogen, stirring, heating to 150 ℃, adding 0.5 part of epoxypropane to initiate reaction, starting to continuously add the rest 34.5 parts of epoxypropane when the temperature rise speed in the reaction kettle exceeds 0.1 ℃/s and the pressure begins to drop, keeping the temperature at 150 ℃ after the addition is finished, curing for 2 hours, keeping the pressure unchanged, vacuumizing and degassing for 20 minutes to obtain a monosilicon alkyl polyether intermediate;
s2: reducing the temperature in a high-pressure glass reaction kettle to 90 ℃, transferring all monosiloxyl polyether intermediates prepared in the step S1 into a normal-pressure reaction kettle, adding 200ppm of stannous octoate-triethylene diamine composite catalyst, heating while stirring, after 10 minutes, heating to 90 ℃, then dropwise adding 0.5 part of toluene diisocyanate, preserving the temperature for 1 hour to obtain triethoxysilane end-capped resin, discharging and filling; sampling the finished product, and measuring infrared without NCO characteristic peak.
Under the process conditions, the mass ratio of stannous octoate to triethylene diamine in different stannous octoate-triethylene diamine composite catalysts is selected, and the dynamic viscosity of the obtained triethoxy silane terminated resin is shown in table 2:
TABLE 2 dynamic viscosity test results of silane-terminated resins for sealants prepared by different mass ratios of stannous octoate to triethylenediamine in stannous octoate-triethylenediamine composite catalysts
Wherein, after the heat preservation for 1h in the example numbers of example 2-3 and example 2-4, the characteristic peak of NCO is measured by an infrared spectrometer (BRUKER: TENSOR27), and the kinetic viscosity is reduced probably due to the formation of
Application experiments show that a small amount of the structure can increase the strength of the silane-terminated resin, because part of the structure reacts with an aminosilane coupling agent in a downstream formula in the cross-linking process and plays an anchoring role in bonding with a substrate.
Example 3
A silane end-capped resin for a sealant is prepared by the following steps:
s1: sequentially adding 1 part of hydroxymethyl triethoxysilane and 80ppm Double Metal Cyanide (DMC) catalyst into a 2.5L high-pressure glass reaction kettle, completely replacing air in the high-pressure glass reaction kettle with nitrogen, stirring and heating to 150 ℃, adding 0.5 part of epoxypropane to initiate reaction, starting to continuously add the rest epoxypropane when the temperature rise speed in the reaction kettle exceeds 0.1 ℃/s and the pressure begins to fall, keeping the temperature at 150 ℃ after the addition is finished, curing for 2 hours, keeping the pressure unchanged, vacuumizing and degassing for 20 minutes to obtain a monosilicon alkyl polyether intermediate;
s2: reducing the temperature in a high-temperature glass reaction kettle to 90 ℃, transferring all monosiloxyl polyether intermediates prepared in the step S1 into a normal-pressure reaction kettle, adding 200ppm of a stannous octoate-triethylene diamine composite catalyst (the mass ratio of stannous octoate to triethylene diamine is 1:0.4), heating while stirring, after 10 minutes, raising the temperature to 90 ℃, then beginning to dropwise add 0.55 part of toluene diisocyanate, after the dropwise addition of the toluene diisocyanate is completed, carrying out heat preservation reaction for 1 hour to obtain triethoxysilane end-capped resin, discharging and filling.
Under the above process conditions, different amounts of propylene oxide were added to obtain triethoxysilane-terminated resins of different number average molecular weights, whose molecular coefficients and dynamic viscosities are shown in table 3:
TABLE 3 dynamic viscosity test results for silane terminated resins prepared with varying amounts of sealant silicone oxide
Example 4
A preparation method of silane end-capped resin for sealant comprises the following steps:
s1: sequentially adding 1 part of hydroxymethyl trimethoxy silane and 80ppm of Double Metal Cyanide (DMC) catalyst into a 2.5L high-pressure glass reaction kettle, completely replacing air in the reaction kettle with nitrogen, stirring and heating to 150 ℃, adding 0.5 part of propylene oxide, exciting the reaction, starting to continuously add the remaining 174.5 parts of propylene oxide when the temperature rise speed in the reaction kettle exceeds 0.1 ℃/s and the pressure begins to fall, preserving heat and curing for 2 hours at 150 ℃ after the addition, keeping the pressure unchanged, vacuumizing and degassing for 20 minutes to obtain a monosilicon alkyl polyether intermediate;
s2: reducing the temperature in a high-pressure glass reaction kettle to 90 ℃, transferring all polymer intermediates obtained in S1 into a normal-pressure reaction kettle, adding 200ppm of stannous octoate-triethylene diamine composite catalyst (the mass ratio is 1:0.4), heating while stirring, increasing the temperature to 90 ℃ after 10 minutes, then beginning to dropwise add 0.55 parts of toluene diisocyanate, after the dropwise addition of the toluene diisocyanate is completed, carrying out heat preservation reaction for 1 hour to obtain trimethoxy silane end-capped resin with the number average molecular weight of 20000, discharging and filling.
The silane-terminated polymer product obtained in this example was tested to have a molecular distribution coefficient of 1.091 and a kinematic viscosity of 28900 mPas (25 ℃).
Comparative example 1
The silane end-capped resin for the sealant is prepared by adopting the conventional process, and the preparation method comprises the following steps:
adding 600g of polyether polyol into a normal-pressure reaction kettle, heating to 110 ℃, stirring, vacuumizing, dehydrating, degassing for 3 hours, cooling to 40 ℃, adding 10.44g of toluene diisocyanate, and carrying out reaction polymerization for 3 hours at a reaction temperature of 80 ℃ to obtain 610.44g of polyurethane prepolymer; wherein the functionality of the polyether polyol is 2, and the number average molecular weight is 20000; and reacting the polyurethane prepolymer with 12.6g of gamma-aminopropyl trimethoxy silane at 80 ℃ for 2-3 hours under the stirring state to obtain trimethoxy silane end-capped resin with the molecular weight of about 20000.
The product of this example, trimethoxy silane-terminated resin, had a molecular distribution coefficient of 1.180 and a dynamic viscosity of 35200 mPas (25 ℃ C.).
Examples 3 to 4, example 4 and comparative example 1 were subjected to a dynamic viscosity test, and the test results are shown in table 4.
TABLE 4 dynamic viscosity test results of silane-terminated resins for sealants of examples 3 to 4, example 4, and comparative example 1
| Example numbering | Examples 3 to 4 | Example 4 | Comparative example 1 |
| Theoretical number average molecular weight | 20000 | 20000 | 20000 |
| Coefficient of molecular distribution | 1.095 | 1.091 | 1.180 |
| Kinematic viscosity (25 ℃, Pa s) | 29120 | 28900 | 35200 |
As can be seen from Table 4, the silane terminated compound resin with the same number average molecular weight and the product prepared by the preparation method provided by the invention have the molecular distribution coefficient less than 1.10 and the dynamic viscosity is obviously reduced.
Example 5
A preparation method of silane modified polyether sealant comprises the following steps:
1. preparing 20% of resin, 17.0% of plasticizer, 2.0% of water removing agent, 57.0% of heavy calcium carbonate, 1.5% of light calcium carbonate, 1.5% of coupling agent and 0.1% of catalyst according to mass percentage; wherein the resin is the triethoxysilane-terminated resin prepared in examples 3-4;
2. mixing production is carried out by using a double planetary mixer: proportionally adding light calcium, heavy calcium, resin, a coupling agent and a plasticizer into a material cylinder, and uniformly stirring;
3. adding a water removing agent, and stirring at a high speed until the mixture is uniformly dispersed, so that the mixed material in the material cylinder has no particles;
4. heating to 100 ℃ and 150 ℃, vacuumizing and preserving heat for 1-3 h;
5. cooling to 30-60 deg.C, and stopping vacuum-pumping;
6. adding catalyst, stirring and defoaming to obtain the product.
Example 6
This example differs from example 5 in that the resin used was the trimethoxysilane terminated resin prepared in example 4.
Comparative example 2
This comparative example differs from example 5 in that the resin used was the silane-terminated resin prepared in comparative example 1.
The silane modified polyether sealants prepared in the examples 5 and 6 and the comparative example 2 are subjected to related performance tests, wherein the performance and the method of the tests are respectively as follows:
extrudability: the determination is carried out according to the method specified in GB 16776-2005 silicone structural sealant for buildings;
surface drying time: according to GB/T13477.5-2002-test method for building sealant material part 5: measurement of surface drying time "by the 8.2B method;
tensile strength: the determination is carried out according to the specified method of GB/T528-2009-determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber-;
elongation at break: GB/T528-2009-determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber, which is obtained by testing of a TMS-8201 universal material testing machine;
hardness: according to GBT 531.1-2008 "method for press-in hardness testing of vulcanized rubber or thermoplastic rubber part I: shore Durometer method (Shore hardness) was performed.
The results of the above performance tests are shown in Table 5.
TABLE 5 results of performance tests related to the sealants prepared in example 5, example 6 and comparative example 2
As can be seen from table 5, the extrusion performance of the sealant prepared from the silane-terminated resin prepared by the method of the present invention and the sealant prepared from the silane-terminated resin prepared by the existing method are improved by 30%, and other various performances are also improved, which indicates that the silane-terminated resin provided by the present invention has low dynamic viscosity and has significant advantages when used for preparing the sealant; the preparation method of the silane-terminated resin provided by the invention has the advantages that the reaction path is reduced, so that the side reaction is reduced, the utilization rate of raw materials is improved, the energy consumption generated in the reaction process can be reduced, and the preparation process is simple and environment-friendly; in addition, the production cost can be greatly reduced by selecting conventional raw materials.
While the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of silane-terminated resin for sealant is disclosed, wherein the structural formula of the silane-terminated resin for sealant is as follows:
wherein R is linear C1-C10 alkyl or branched C3-C10 alkyl;
R0is a linear C1-C10 alkyl group, a branched C3-C10 alkyl group or a branched C3-C10 alkoxy group;
R1is a linear C1-C10 alkyl group or a branched C3-C10 alkyl group;
R2is a diisocyanate residue;
the R is2Is composed of
Or C6H12One of (1); the number average molecular weight of the silane end-capped resin for the sealant is 4000-20000;
the method is characterized by comprising the following steps:
s1: adding a first catalyst into hydroxyl alkoxy silane serving as a raw material, heating after nitrogen is placed, then introducing an epoxy compound for pre-reaction, continuously introducing the epoxy compound for reaction after the initiation reaction to obtain a monosiloxane terminated polyether intermediate, wherein the hydroxyl alkoxy silane is hydroxymethyl triethoxysilane or hydroxymethyl trimethoxysilane;
s2: and adding a second catalyst and diisocyanate into the monosiloxane terminated polyether intermediate formed in the step S1, and keeping the temperature for continuous reaction to obtain the silane terminated resin for the sealant.
2. The method of claim 1, wherein the molar ratio of epoxy compound to hydroxyalkoxysilane is from 35 to 280: 1.
3. the method of claim 1 wherein the molar ratio of diisocyanate to the monosiloxanyl polyether intermediate in S2 is from 0.4 to 0.6: 1.
4. the method of claim 1, wherein the first catalyst is an alkoxylation catalyst.
5. The method of claim 4 wherein the alkoxylation catalyst is a double metal cyanide catalyst.
6. The method of claim 1, wherein the epoxy compound is ethylene oxide and/or propylene oxide.
7. The method for preparing the silane terminated resin for sealant according to claim 1, wherein the mass of the second catalyst is 200-500ppm of the total amount charged in the S1.
8. The method for preparing the silane-terminated resin for sealants according to claim 7, wherein the second catalyst is a stannous octoate-triethylenediamine composite catalyst, and the mass ratio of the components is 1: 0.4-0.8.
9. The method for producing the silane-terminated resin for sealants according to claim 1, wherein the diisocyanate is one or a mixture of two or more of toluene diisocyanate, 1, 5-naphthalene diisocyanate, hydrogenated phenylmethane diisocyanate, and 1, 6-hexamethylene diisocyanate.
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| CN115260449B (en) * | 2022-08-19 | 2023-08-01 | 合肥工业大学 | Polyurethane anchoring agent with low slurry viscosity and high anchoring body strength and preparation method thereof |
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| DE102008000903A1 (en) * | 2008-04-01 | 2009-10-08 | Evonik Goldschmidt Gmbh | New polyether alcohols carrying organosiloxane groups by alkoxylation of epoxide-functional (poly) organosiloxanes on double metal cyanide (DMC) catalysts, and also processes for their preparation |
| DE102010038768A1 (en) * | 2010-08-02 | 2012-02-02 | Evonik Goldschmidt Gmbh | Modified alkoxylation products having at least one non-terminal alkoxysilyl group with increased storage stability and increased extensibility of the polymers prepared using them |
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| EP2805985A1 (en) * | 2013-05-22 | 2014-11-26 | Sika Technology AG | Polymer containing hydroxysilane and silane groups |
| KR20180018091A (en) * | 2016-08-12 | 2018-02-21 | 박재준 | Synthesizing method for nanosilica treated with epoxy-terminated silicone and epoxy/nanocomposite with the siliconemodified nanosilica for outdoor electrical insulator |
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